Method for processing silver halide color photographic light-sensitive materials

ABSTRACT

The present invention relates to a method for bleaching a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing silver iodobromide after color-developing it. The object of the present invention is to speed up the bleaching treatment in the aforesaid method and to reduce the amount of waste liquor from the bleaching treatment. The present invention is characterized in that the bleaching is performed in the presence of a bleaching accelerator and that it is carried out while a bleaching solution is brought into contact with an anion-exchange resin.

TECHNICAL FIELD

The present invention relates to a method for processing silver halidecolor photographic light-sensitive materials having silver halideemulsion layers containing silver iodobromide and more specifically to amethod for processing such photographic light-sensitive materialscomprising a desilvering step in which the light-sensitive materials arerapidly bleached while reducing the amount of waste liquor derived fromthe bleaching treatment.

TECHNICAL BACKGROUND

In general, the basic processes for processing color light-sensitivematerials are a color developing process and a desilvering process. Inthe color developing process, the silver halide exposed to light isreduced with a color developing agent to form elemental silver andsimultaneously the oxidized color developing agent reacts with acoloring agent (coupler) to form dye images. In the subsequentdesilvering process, the elemental silver formed during the colordeveloping process is oxidized by the action of an oxidizing agent (ingeneral, referred to as "bleaching agent") and then is dissolved by theaction of a complexing agent for silver ions generally referred to as"fixing agent". Only the dye images remain on the color light-sensitivematerials after the desilvering process.

The desilvering process described above generally comprises twoprocessing baths, one of which is a bleaching bath containing ableaching agent and the other of which is a fixing bath containing afixing agent; or only one bath simultaneously containing a bleachingagent and a fixing agent.

The practical development processing further comprises, in addition tothe foregoing basic processes, a variety of auxiliary processes for thepurposes of maintaining photographic and physical properties of images,enhancing storability of images or the like. Examples of such auxiliaryprocesses are a film hardening bath, a stopping bath, an imagestabilizing bath and a water washing bath.

The bleaching agents used in the desilvering process are in general redprussiate of potash, bichromates, ferric chloride, ferric complexes ofaminopolycarboxylic acids and persulfates.

However, a problem of environmental pollution arises when red prussiateof potash and bichromates are employed and the use thereof requires aspecific installation for processing the same. In addition, if theferric chloride is used, it accompanies the formation of iron hydroxideand the generation of stains during the subsequent water washingprocess. Thus, it is difficult to practically use such bleaching agentsbecause of various practical obstacles mentioned above. Regarding thepersulfates, the bleaching ability thereof is very weak and it takes along period of time for bleaching. To eliminate this problem, there isproposed a method in which a bleaching accelerator is simultaneouslyused for enhancing the bleaching ability. However, the persulfates perse is specified as dangerous materials in accordance with the FireServices Act. The use thereof is restricted, it is needed to takevarious steps in storing the same and thus practical use thereof is verydifficult.

One the other hand, ferric complexes of aminopolycarboxylic acids, inparticular ferric complex of ethylenediaminetetraacetic acid and ferriccomplex of diethylenetriaminepentaacetic acid have widely been used as ableaching agent since they cause no environmental pollution and noproblem of storage as in the case of persulfates. However, the ferriccomplexes of aminopolycarboxylic acids do not exhibit sufficientbleaching ability. A low sensitive silver halide color light-sensitivematerial mainly composed of a silver chlorobromide emulsion can bebleached with a solution containing such a ferric complex as a bleachingagent. But, if it is intended to process a highly sensitive colorlight-sensitive material which is mainly composed of a silverchloroiodobromide or silver iodobromide emultion and which is sensitizedwith a color sensitizer, in particular a photographic color reversallight-sensitive material and a photographic color negativelight-sensitive material in which an emulsion having a high silvercontent is used, the desilvering is insufficient and it takes a longtime for performing bleaching.

For instance, if a photographic color negative light-sensitive materialis bleached with a bleaching solution containing a ferric complex ofaminopolycarboxylic acid, the required bleaching time is at least 4minutes and complicated operations such as the control of the pH valueof the bleaching solution and aeration process are necessary to hold thebleaching ability thereof. Even when such complicated operations arepractically performed, insufficient bleaching is often observed.

Moreover, the bleaching process must be followed by processing with afixing solution for at least 3 minutes, which leads to furtherelongation of the desilvering process. Therefore, there is a demand forreducing the processing time.

Particularly, minilab processing has recently spread and, therefore,reduction of processing time is quite important to improve theefficiency of the minilab and to provide users with quick services.However, it is found that the reduction of time required for adesilvering step causes difficulties on improvement of the desilveringspeed and raises stain (Dmin) of processed light-sensitive materials.Among them, increase in the magenta stain is remarkable.

It is also required to reduce the amount of waste liquor derived fromphotographic processing from the viewpoint of preventing environmentalpollution and, in the desilvering process, it becomes an importantsubject to reduce the amount of waste liquor or to reduce the amount ofa bleach-fixing solution to be replenished.

German Patent No. 866,605 discloses a bleach-fixing solution containinga ferric complex of aminopolycarboxylic acid and a thiosulfate in onesolution to make the disilvering process more rapid. However, if aferric aminopolycarboxylate which inherently exhibits low oxidationability (bleaching ability) coexists with a thiosulfate having reducingability, the bleaching ability thereof is extremely lowered and thus itcannot practically be used as a bleach-fixing solution for sufficientlydesilvering highly sensitive photographic color light-sensitivematerials having a high silver content. There has been proposed variousmethods for eliminating such drawbacks of the bleach-fixing solution,for instance, a method in which an iodide or bromide is added thereto asdisclosed in U.K. Patent No. 926,569 and Japanese Patent Publication forOpposition Purpose (hereunder referred to as "J.P. KOKOKU") No.53-11854; a method in which a ferric aminopolycarboxylate is containedin a high content using a triethanolamine as disclosed in JapanesePatent Unexamined Publication (hereunder referred to as "J.P. KOKAI")No. 48-95834. However, these methods do not provide sufficient effectsand, therefore, they cannot practically be employed.

In addition to the insufficient desilvering, the bleach-fixing solutionhas a further severe problem that cyan dyes formed during colordevelopment are reduced by the solution to form leuco dyes and to thusimpair color reproduction of the light-sensitive material. As discussedin the specification of U.S. Pat. No. 3,773,510, it is known that thisproblem can be solved by increasing the pH value of the bleach-fixingsolution. However, as pH increases, the bleaching ability on thecontrary is extremely lowered and thus the increase in the pH valuecannot practically be adopted. U.S. Pat. No. 3,189,452 discloses amethod for oxidizing the leuco dyes with a bleaching solution containingred prussiate of potash to convert them into cyan dyes, after thebleach-fixing process. However, the use of red prussiate of potashcauses the environmental pollution and even if the light-sensitivematerials are additionally bleached after the bleach-fixing process, itis almost impossible to reduce the amount of silver.

By the way, there have been conducted various studies to develop a meansfor recovering silver as a valuable noble metal from bleach-fixingand/or fixing solutions, for instance, a method for recovering silver byintroducing a bleach-fixing solution in an electrolytic cell and thenelectrolyzing it; a method for recovering silver by diluting thebleach-fixing solution to lower the solubility of a silver salt toprecipitate the same; a method for recovering silver by adding sodiumsulfide to those solutions in order to form silver sulfide; or a methodfor recovering silver, in the form of ions, by passing the bleach-fixingsolution through a column packed with a large amount of an ion-exchangeresin. Such means for recovering silver are detailed in, for instance,Kodak Publication, J-10 (Recovering Silver From Photographic Materials),issued by Kodak Industrial Division; J.P. KOKOKU No. 58-22528; J.P.KOKAI No. 54-19496; Belgian Patent No. 869,087; and DEOS No. 2,630,661.

However, these methods are developed to recover silver frombleach-fixing solutions, but not to reuse the solutions obtained afterthe recovery of silver. Therefore, there are various obstacles to reusesuch bleach-fixing solutions after desilvering. For instance, thebleach-fixing solutions obtained after desilvering cannot be reused orit is necessary to add components which are lost during the recovery ofsilver to reuse the same (addition of a regenerant). As described above,it has not yet been realized to simultaneously reduce the amount ofwaste liquor and rapidly carry out the desilvering process whilerecovering silver.

Accordingly, an object of the present invention is to provide a methodfor processing silver halide color photographic light-sensitivematerials, which comprises a rapid bleaching process capable of reducingthe amount of waste bleaching solution.

Further, an object of the present invention is to provide a method forprocessing silver halide color photographic light-sensitive materials,which comprises a rapid bleaching process capable of reducing the stain.

The aforementioned objects of the present invention can effectively beachieved by providing a method which comprises the steps of colordeveloping a silver halide color photographic light-sensitive materialhaving at least one silver halide emulsion layer containing silverbromoiodide on a substrate and then desilvering the same. The method ischaracterized in that the bleaching process is carried out in thepresence of a bleaching accelerator and that the bleaching process iscarried out while a part or whole of a bleaching solution is broughtinto contact with a strong basic anion-exchange resin.

The inventors of this invention have conducted various studies and havefound that a bleaching solution deteriorated due to processing ofphotographic light-sensitive materials containing silver iodidecomprises a large amount of silver ions and a small amount of iodideions and that the bleaching ability thereof is extremely lowered due tothe presence of both these ions. However, if silver ions present in thedeteriorated bleaching solution are recovered by any means forrecovering silver as described above, the thiosulfate serving as afixing agent or sulfite ions serving as a preservative thereof aredecomposed or removed during the recovery of silver.

Contrary to this, the inventors of this invention have found that thebleaching ability of the solution can be recovered by removing iodideions present in a small amount, although silver ions are still presenttherein and that the iodide ions can selectively be removed from thedeteriorated bleaching solution by bringing it into contact with ananion-exchange resin.

It has been un-expected that the bleach-accelerating action is extremelyimproved by using a bleaching accelerator, particularly an organicbleaching accelerator when iodide ions in the bleaching solution arereduced by the method of the present invention. This effect isremarkable when the amount of iodide ions is 0.5 g/l or less,particularly 0.3 g/l or less, expressed in the amount of KI.

As mentioned above, the amount of iodide ions can be reduced and as aresult, the replenishing amount of the bleaching solution can be reducedand, at the same time, the amount of the waste solution can be reduced.Whereby it becomes possible to provide a rapid bleaching processing withlow-cost and low probability of environmental pollution.

The light-sensitive materials which are processed by the method of thepresent invention comprises at least one silver halide emulsion layercontaining at least one mole % of silver iodide, preferably 5 to 25 mole% and more preferably 7 to 20 mole %.

Therefore, in the method of this invention, there may be processed acolor light-sensitive material comprising a substrate provided thereonwith at least one layer of silver halide emulsion which contains atleast one silver iodide selected from the group consisting of silveriodide, silver iodobromide, silver chloroiodobromide and silverchloroiodide. In this respect, silver chloride and silver bromide mayoptionally be used in addition to the foregoing silver iodide.

The silver halide grains used in the color photographic light-sensitivematerials processed by the method of the invention may be in anycrystalline forms such a regular crystalline form as a cubic,octahedral, rhombododecahedral or tetradecahedral form; such anirregular form as a spheric or tabular form; or a composite formthereof. In addition, they may be tabular grains having an aspect ratioof not less that 5 as disclosed in Research Disclosure, Vol. 225, pp.20-58 (January, 1983).

The silver halide grains may be those having epitaxial structure orthose having a multilayered structure whose internal composition (suchas halogen composition) differs from that of the surface region.

The average grain size of silver halide is preferably not less than0.5μ, more preferably in the range of 0.7 to 5.0μ.

The grain size distribution thereof may be either wide or narrow. Theemultions comprising a silver halide having a narrow grain sizedistribution is known as so-called monodisperse emulsions whosedispersion coefficient is preferably not more than 20% and morepreferably not more than 15%. The "dispersion coefficient" herein meansthe standard deviation divided by the average grain size.

The photographic emulsions may comprise any combination of silverchloride, silver bromide, silver iodide, silver iodobromide, silverchloroiodobromide and silver chloroiodide.

The coated amount of silver in the light-sensitive materials processedby the invention is generally 1 to 20 g/m², preferably 2 to 10 g/m²,provided that the total amount of iodine (AgI) present in the silverhalide light-sensitive materials is preferably not less than 4×10⁻³mole/m² and more preferably 6×10⁻³ to 4×10⁻² mole/m².

The effect of the invention is insufficient when the amount of silvercoated on a light-sensitive material is less than 2 g/m². The use ofmore than 10 g/m² of silver makes the bleaching power (desilvering)insufficient and may give an unsatisfactory result.

The silver halide emulsions may contain other salts or complexes such ascadmium salts, zinc salts, lead salts, thallium salts, iridium salts orcomplex salts thereof, rhodium salts or complex salts thereof and ironsalts or complex salts thereof, which are added thereto during theformation of silver halide grains or a physical ripening process.

The bleaching accelerators, preferably organic bleaching accelerators,which are added to a bleaching bath, the bath preceeding it or thelight-sensitive layer may be selected from compounds having mercaptogroups or disulfide bonds; thiazolidine derivatives, thioureaderivatives and isothiourea derivatives, so far as they show a bleachingacceleration effect and preferred examples thereof are those representedby the following general formula (IA) to (VIA):

    R.sup.1A --S--M.sup.1A                                     (IA)

In the general formula, M^(1A) represents a hydrogen atom, an alkalimetal atom or an ammonium residue; and R^(1A) represents an alkyl,alkylene, aryl or heterocyclic group. Preferably the alkyl group has 1to 5, more preferably 1 to 3 carbon atoms. The alkylene group preferablyhas 2 to 5 carbon atoms. Examples of the aryl group include phenyl andnaphthyl groups, preferably phenyl group. Preferred examples of theheterocyclic groups include nitrogen atom-containing 6-membered ringssuch as pyridine and triazine; and nitrogen atom-containing 5-memberedrings such as azole, pyrazole, triazole and thiazole. Particularlygroups containing at least two nitrogen atoms as ring-forming atoms aremore preferred. R^(1A) may be substituted with substituents. Examples ofsuch substituents are alkyl, alkylene, alkoxy, aryl, carboxyl, sulfo,amino, alkylamino, dialkylamino, hydroxyl, carbamoyl, sulfamoyl andsulfonamido groups.

Preferred compounds represented by the general formula (IA) are thoserepresented by the following general formulas (IA-1) to (IA-4): ##STR1##

In the formula, R^(2A), R^(3A) and R^(4A) may be the same or differentand each represents a hydrogen atom, a substituted or unsubstitutedlower alkyl group (preferably those having 1 to 5 carbon atoms, inparticular a methyl, ethyl or propyl group) or an acyl group (preferablythose having 1 to 3 carbon atoms, such as an acetyl or propionyl group)and kA is an integer of 1 is 3. Z^(1A) represents an anion such aschloride ion, bromide ion, nitrate ion, sulfate ion, p-toluenesulfonateion or oxalate ion. hA is 0 or 1 and iA is 0 or 1.

R^(2A) and R^(3A) may be bonded together to form a ring. Particularlypreferred group R^(2A), R^(3A) or R^(4A) is a substituted orunsubstituted lower alkyl group.

Examples of substituents of R^(2A), R^(3A) and R^(4A) are hydroxyl,carboxyl, sulfo and/or amino groups. ##STR2##

In the general formulas, R^(5A) represents an hydrogen atom, a halogenatom such as a chlorine or bromine atom, an amino group, a substitutedor unsubstituted lower alkyl group preferably having 1 to 5 carbon atoms(particularly, a methyl, ethyl or propyl group), an amino group havingalkyl group(s) such as a methylamino, ethylamino, dimethylamino ordiethylamino group, or a substituted or unsubstituted alkylthio group.

Examples of substituents of R^(5A) are a hydroxyl group, a carboxylgroup, a sulfo group, an amino group, or an amino group having an alkylgroup.

    R.sup.1A --S--S--R.sup.6A                                  (IIA)

In the formula, R^(1A) is the same as that in the general formula (IA)and R^(6A) has the same meaning as that of R^(1A). R^(1A) and R^(6A) maybe the same or different.

Preferred compounds represented by formula (IIA) are those representedby the following general formula (IIA-1): ##STR3##

In the formula, R^(7A), R^(8A) and R^(9A) have the same meanings asR^(2A), R^(3A) and R^(4A) defined above. hA, kA and Z^(1A) are the sameas those in formula (IA-1). iB is 0, 1 or 2. ##STR4##

In formula (III), R^(10A) and R^(11A) may be the same or different andeach represents a hydrogen atom, an alkyl group optionally havingsubstituents, preferably a lower alkyl group such as a methyl, ethyl orpropyl group, a phenyl group optionally having substituents, aheterocyclic group optionally having substituents, more specifically aheterocyclic group including at least one hetero atom selected from thegroup consisting of nitrogen, oxygen, sulfur atoms or the like, such asa pyridine ring, a thiophene ring, a thiazolidine ring, a benzoxazolering, a benzotriazole ring, a thiazole ring and an imidazole ring;R^(12A) represents a hydrogen atom or a lower alkyl group optionallyhaving substituents such as a methyl or ethyl group, preferably thosehaving 1 to 3 carbon atoms. Examples of substituents of R^(10A) toR^(12A) are a hydroxyl group, a carboxyl group, a sulfo group, an aminogroup and a lower alkyl group. R^(13A) represents a hydrogen atom, analkyl group or a carboxyl group. ##STR5##

In formula (IVA), R^(14A), R^(15A) and R^(16A) may be the same ordifferent and each represents a hydrogen atom or a lower alkyl groupsuch as a methyl or ethyl group, preferably those having 1 to 3 carbonatoms. kB is an integer of 1 to 5.

X^(1A) represents an amino group optionally having substituents, a sulfogroup, a hydroxyl group, a carboxyl group or a hydrogen atom. Examplesof the substituents include substituted or unsubstituted alkyl groups(e.g., methyl, ethyl, hydroxyalkyl, alkoxyalkyl and carboxyalkyl groups)and two alkyl groups may be bonded together to form a ring. R^(14A),R^(15A) and R^(16A) may be bonded together to form a ring. Preferredexamples of R^(14A) to R^(16A) are a hydrogen atom, a methyl group or anethyl group; those of X_(1A) include an amino group or a dialkylaminogroup. ##STR6##

In formula (VA), A^(1A) is an aliphatic linking group, an aromaticlinking group or a heterocyclic linking group with a valency of n,wherein A^(1A) is simply an aliphatic, aromatic or heterocyclic groupwhen n is 1.

Alkylene groups having 3 to 12 carbon atoms such as trimethylene,hexamethylene, cyclohexylene are exemplified as the aliphatic linkinggroup represented by A^(1A).

Examples of the aromatic linking groups include arylene groups having 6to 18 carbon atoms such as phenylene and naphthylene groups.

Examples of the heterocyclic linking groups include heterocyclic groupscomprising at least one hetero atom such as oxygen, sulfur and nitrogenatom (e.g., thiophene, furantriazine, pyridine and piperidine).

Generally, the aliphatic, aromatic or heterocyclic linking groupcomprises a single group, but they may be those comprising two or moreof these bonded together directly or through a bivalent linking group(e.g., --O--, --S--, R^(20A) N<, --SO₂ --, --CO-- or those formed bycombining these groups; R^(20A) represents a lower alkyl group).

These aliphatic, aromatic and heterocyclic linking groups may havesubstituents.

Examples of such substituents are alkoxy groups, halogen atoms, alkylgroups, hydroxyl group, carboxyl group, sulfo group, sulfonamido groupand sulfamoyl group.

X^(2A) represents --O--, --S--, R^(21A) --N< (wherein R^(21A) is a loweralkyl group such as a methyl or ethyl group); R^(17A) and R^(18A) eachrepresents a substituted or unsubstituted lower alkyl group (e.g.,methyl, ethyl, propyl, isopropyl or pentyl group) and preferred examplesof the substituents are hydroxyl, lower alkoxy groups such as methoxy,methoxyethoxy and hydroxyethoxy groups, amino groups such asunsubstituted amino, dimethylamino and N-hydroxyethyl-N-methylaminogroups. If there are two or more substituents, they may be the same ordifferent.

R^(19A) represents a lower alkylene group having 1 to 5 carbon atomssuch as methylene, ethylene, trimethylene and methylmethylene; Z^(2A)represents an anion such as a halide ion (e.g., a bromide or chlorideion), a nitrate ion, a sulfate ion, p-toluenesulfonate ion or an oxalateion.

R^(17A) and R^(18A) may be linked through a carbon or hetero atom (suchas oxygen, nitrogen or sulfur atom) to form a 5- or 6-memberedheterocyclic ring such as a pyrrolidine, piperidine, morpholine,triazine or imidazolidine ring.

R^(17A) (or R^(18A)) and A may be linked through a carbon or hetero atom(such as an oxygen, nitrogen or sulfur atom) to form a 5- or 6-memberedheterocyclic ring such as a hydroxyquinoline, hydroxyindole orisoindoline ring.

Moreover, R^(17A) (or R^(18A)) and R^(19A) may be linked through acarbon or hetero atom (such as oxygen, nitrogen or sulfur arom) to forma 5- or 6-membered heterocyclic ring such as a piperidine, pyrrolidineor morpholine ring.

lA is 0 or 1; mA is 0 or 1; nA is 1, 2 or 3; pA is 0 or 1; and qA is 0,1, 2 or 3. ##STR7##

In the formula, X^(1A) and kB are the same as those in the generalformula (IVA).

M^(2A) represents a hydrogen atom, an alkali metal atom, an ammonium or--S--CS--NR^(22A) --(CH₂)kB--X^(1A) wherein R^(22A) represents ahydrogen atom or a lower alkyl group which has 1 to 5 carbon atoms andmay be substituted.

Specific examples of the compounds represented by formulas (IA) to (VIA)are as follows: ##STR8##

Biscations and bisamines as disclosed in J.P.A. (Japanese PatentApplication Serial) Nos. 62-143467, 62-185030, 62-185031, 62-274094,62-274095 and 62-277580 can be used as bleaching accelerators inaddition to the foregoing compounds.

The above listed compounds may be prepared according to any knownmethods. More specifically, compounds (I) may be prepared by the methoddisclosed in U.S. Pat. No. 4,285,984; G. Schwarzenbach et al., Helv.Chim. Acta, 1955, Vol. 38, p. 1147; and R. O. Clinton et al., J. Am.Chem. Soc., 1948, Vol. 70, p. 950; compounds (II) by the methoddisclosed in J.P. KOKAI No. 53-95630; compounds (III) and (IV) by themethod disclosed in J.P. KOKAI No. 54-52534; compounds (V) by the methoddisclosed in J.P. KOKAI Nos. 51-68568, 51-70763 and 53-50169; compounds(VI) by the method disclosed in J.P. KOKOKU No. 53-9854 and J.P. KOKAINo. 59-214855; and compounds (VII) by the method disclosed in J.P. KOKAINo. 53-94927.

The amount of the bleaching accelerators to be added to the bleachingsolution used in the invention may vary depending on the kinds of thephotographic light-sensitive materials to be processed, processingtemperature, processing time of the intended process and the like, butit is desirably in the range of 1×10⁻⁵ to 1×10⁻¹ mole, preferably 1×10⁻⁴to 5×10⁻² mole per liter of the bleaching solution.

These compounds may in general be added to the bleaching solution in theform of a solution in water, an alkaline solution, an organic acid or anorganic solvent. Alternatively, it is also possible to directly addpowder to the bleaching solution without impairing their effect ofaccelerating bleaching process.

In the present invention, any commercially available resins may be usedas the anion-exchange resins. Particularly, a basic anion-exchange resinis preferably used as the anion-exchange resins of the presentinvention.

Preferred basic anion-exchange resins used in the invention arerepresented by the formula (VIII): ##STR9##

In the formula, A represents a monomer unit obtained by copolymerizingcopolymerizable monomers having at least two ethylenically unsaturatedcopolymerizable groups and at least one of these groups is present in aside chain. B represents a monomer unit obtained by copolymerizingethylenically unsaturated copolymerizable monomers. R¹³ represents ahydrogen atom, a lower alkyl group or an aralkyl group.

Q represents a single bond, or an alkylene group, a phenylene group, anaralkylene group ##STR10## Wherein L represents an alkylene, arylene oraralkylene group and R is an alkyl group.

G represents ##STR11## and R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ maybe the same or different and may be substituted and each represents ahydrogen atom, an alkyl, anyl or aralkyl group. X⁻ represents an anion.Two or more groups selected from Q, R₁₄, R₁₅ and R₁₆ or Q, R₁₇, R₁₈,R₁₉, R₂₀ and R₂₁ may be bonded to form a ring structure together withthe nitrogen atom.

x, y and z each represents molar percentage, x ranges from 0 to 60, yfrom 0 to 60 and z from 30 to 100.

The foregoing general formula (VIII) will hereunder be explained in moredetail. Examples of monomers from which A is derived are divinylbenzene,ethylene glycol dimethacrylate, diethylene glycol dimethacrylate,triethylene glycol dimethacrylate, ethylene glycol diacrylate,diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentylgrlycol dimethacrylate and tetramethylene glycol dimethacrylate andparticularly divinylbenzene and ethylene glycol dimethacrylate arepreferred.

A may comprise at least two of the foregoing monomer units.

Examples of ethylenically unsaturated monomer from which B is derivedinclude ethylene, propylene, 1-butene, isobutene, styrene,α-methylstyrene, vinyltoluene, monoethylenically unsaturated esters ofaliphatic acids (e.g., vinyl acetate and allyl acetate), esters ofethylenically unsaturated monocarboxylic acids or dicarboxylic acids(e.g., methyl methacrylate, ethyl methacrylate, n-butyl methacrylate,n-hexyl methacrylate, cyclohexyl methacrylate, bonzyl methacrylate,n-butyl acrylate, n-hexyl acrylate and 2-ethylhexyl acrylate),monoethylenically unsaturated compounds (e.g., acrylonitrile), or dienes(e.g., butadiene and isoprene). Particularly preferred are styrene,n-butyl methacrylate and cyclohexyl methacrylate. B may comprise two ormore of the foregoing monomer units.

R₁₃ preferably represents a hydrogen atom, a lower alkyl group having 1to 6 carbon atoms such as a methyl, ethyl, n-propyl, n-butyl, n-amyl orn-hexyl group or an aralkyl group such as a benzyl group andparticularly preferred are a hydrogen atom and a methyl group.

Q preferably represents a divalent optionally substituted alkylene grouphaving 1 to 12 carbon atoms such as a methylene, ethylene orhexamethylene group, an optionally substituted arylene group such as aphenylene group, or an optionally substituted aralkylene group having 7to 12 carbon atoms such as ##STR12## and groups represented by thefollowing ##STR13##

Wherein L preferably represents an optionally substituted alkylene grouphaving 1 to 6 carbon atoms, or an optionally substituted arylene groupor an optionally substituted aralkylene group having 7 to 12 carbonatoms, more preferably an optionally substituted alkylene group having 1to 6 carbon atoms. R is preferably an alkyl group having 1 to 6 carbonatoms.

G represents ##STR14## and R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ maybe the same or different and each represents a hydrogen atom, an alkylhaving 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms or anaralkyl group having 7 to 20 carbon atoms. These alkyl, aryl and aralkylgroups include substituted alkyl, aryl and aralkyl groups.

Examples of alkyl groups include such unsubstituted alkyl groups asmethyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl,n-amyl, iso-amyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl,n-nonyl, n-decyl and n-dodecyl groups. The number of carbon atoms of thealkyl group preferably ranges from 1 to 16 and more preferably 4 to 10.

Examples of substituted alkyl groups are alkoxyalkyl groups such asmethoxymethyl, methoxyethyl, methoxybutyl, ethoxyethyl, ethoxypropyl,ethoxybutyl, butoxyethyl, butoxypropyl, butoxybutyl and vinyloxyethyl;cyanoalkyl groups such as 2-cyanoethyl, 3-cyanopropyl and 4-cyanobutyl;halogenated alkyl groups such as 2-fluoroethyl, 2-chloroethyl and3-fluoropropyl; alkoxycarbonylalkyl groups such asethyoxycarbonylmethyl; allyl group, 2-butenyl group and propargyl.

Examples of aryl groups include such unsubstituted aryl groups as phenyland naphthyl groups; such substituted aryl groups as alkylaryl groups(e.g., 2-methylphenyl, 3-methylphenyl, 4-mehylphenyl, 4-ethylphenyl,4-isopropylphenyl and 4-t-butylphenyl); alkoxyaryl groups (e.g.,4-methoxyphenyl, 3-methoxyphenyl and 4-ethoxyphenyl); and aryloxyarylgroups (e.g., 4-phenoxyphenyl). The number of carbon atoms of the arylgroup preferably ranges from 6 to 14, more preferably 6 to 10.Particularly preferred is a phenyl group.

Examples of aralkyl groups include unsubstituted aralkyl groups such asbenzyl, phenethyl, diphenylmethyl and naphthylmethyl; substitutedaralkyl groups such as alkylaralkyl groups (e.g., 4-methylbenzyl,2,5-dimethylbenzyl and 4-isopropylbenzyl), alkoxyaralkyl groups (e.g.,4-methoxybenzyl and 4-ethoxybenzyl), cyanoaralkyl groups (e.g.,4-cyanobenzyl), perfluoroalkoxyaralkyl groups (e.g.,4-pentafluoropropoxybenzyl and 4-undecafluorohexyloxybenzyl) andhalogenoaralkyl groups (e.g., 4-chlorobenzyl, 4-bromobenzyl and3-chlorobenzyl). The number of carbon atoms of the aralkyl grouppreferably ranges from 7 to 15 and more preferably 7 to 11. Among these,benzyl and phenethyl groups are particularly preferred.

R₁₄, R₁₅ and R₁₆ each preferably represents an alkyl or aralkyl group,in particular they represent alkyl groups whose total number of carbonatoms ranges from 12 to 30.

R₁₇ to R₂₁ each preferably represents a hydrogen atom or an alkyl group.

X.sup.⊖ represents an anion such as a hydroxide ion, a halogen ion(e.g., chloride or bromide ion), an alkyl- or arylsulfonate ion (e.g., amethanesulfonate, ethanesulfonate, benzenesulfonate orp-toluenesulfonate ion), an acetate ion, a sulfate ion and a nitrateion. Particularly preferred are chloride, acetate and sulfate ions.

At least two groups selected from Q and R₁₄ to R₁₆ may be preferably bebonded to form a ring structure together with the nitrogen atom.Examples of such rings preferably include pyrrolidine, piperidine,morpholine, pyridine, imidazole and quinuclidine rings. Particularlypreferred are pyrrolidine, morpholine, piperidine, imidazole andpyridine rings.

At least two groups selected from Q and R₁₇ to R₂₁ may be bonded to forma ring structure together with the nitrogen atom. Particularly preferredare 5- or 6-membered ring structures.

The basic anion-exchange resins of the invention may comprise two ormore of the foregoing monomer units: ##STR15##

x ranges from 0 to 60 mole %, preferably 0 to 40 mole %, and morepreferably 0 to 30 mole %. y ranges from 0 to 60 mole %, preferably 0 to40 mole % and more preferably 0 to 30 mole %. z ranges from 30 to 100mole %, preferably 40 to 95 mole % and more preferably 50 to 85 mole %.

Among the compounds represented by formula (VIV), particularly preferredare those represented by the following general formula (IX): ##STR16##

In the formula, A, B, x, y, z, R₁₃ to R₁₆, and X⁻ are the same as thosein the general formula (VIII).

More preferred are those represented by formula (IX) in which all of thegroups R₂ to R₄ are alkyl groups whose total number of carbon atomsranges from 12 to 30.

Specific examples of the basic anion-exchange resins of the presentinvention represented by the general formula (VIII) will be listedbelow, but the compounds of this invention are not restricted to thesespecific examples. ##STR17##

In the present invention, any commercially available resins may be usedas the strong basic anion-exchange resins. Specific examples thereofinclude Amberlite IRA-410, IRA-411, IRA-910, IRA-400, IRA-401, IRA-402,IRA-430, IRA-458, IRA-900, IRA-904 and IRA-938 (all these beingavailable from Rohm & Haas Co., Ltd.); DIAION SA 10A, SA 12A, SA 20A, SA21, PA 306, PA 316, PA 318, PA 406, PA 412 and PA 418 (all these beingavailable from MITSUBISHI CHEMICAL INDUSTRIES LTD.) and EPOLUS K-70(available from MIYOSHI FAT & OIL CO., LTD.).

Moreover, they may be synthesized in accordance with the followingPreparation Examples.

GENERAL METHOD FOR PREPARATION

The anion-exchange resins of this invention can be synthesized byquaternarizing a substantially water-insoluble resin having groupscapable of being quaternarized with a tertiary amine or a tertiaryphosphine (hereunder referred to as a "precarsor resin") with a tertiaryamine or a tertiary phosphine to introduce cations. The precursor resinsmay be prepared by a variety of methods as disclosed in J.P. KOKAI No.59-39347, U.S. Pat. Nos. 2,874,132; 3,297,648; 3,549,562; 3,637,535;3,817,878; 3,843,566; 2,630,427 and 2,630,429; German Patent No.1,151,127 and J.P. KOKOKU Nos. 32-4143, 46-19044, 46-20054, 53-5294,33-2796 and 33-7397 or methods similar thereto.

The introduction of cationic groups into the precursor resin byquaternarization with a tertiary amine or phosphine can be carried outby using the foregoing precursor resin and a tertiary amine or phosphineaccording to methods as disclosed in J.P. KOKAI No. 59-39347; U.S. Pat.Nos. 2,874,132; 3,297,648; 3,549,562; 3,637,535; 3,817,878; 3,843,566;2,630,427; 2,630,429; German Patent No. 1,151,127 and J.P. KOKOKU Nos.32,4143, 46-19044; 46-20054, 53-5294; 33-2796 and 33-7397 or methodssimilar thereto.

Alternatively, the anion-exchange resin of this invention may also beobtained by using a substantially water-insoluble monomer having acopolymerizable ethylenically unsaturated group and a quaternaryammonium or phosphonium group in the foregoing methods for synthesizingthe precursor resins or the methods similar thereto to form a resin.

Further, the anion-exchange resin of this invention may be obtained byusing a monomer mixture of a substantially water-insolublecopolymerizable monomer having a quaternary ammonium or phosphoniumgroup and an ethylenically unsaturated group and a substantiallywater-insoluble copolymerizable monomer having a group capable of beingquaternarized with an amine or phosphine and an ethylenicallyunsaturated group in the foregoing methods for synthesizing theprecursor resin or the methods similar thereto to obtain a resin andthen introducing cations into the precursor resin according to theforegoing methods for quaternarization with a tertiary amine orphosphine or the methods similar thereto.

PREPARATION EXAMPLE 1 Preparation ofpoly(divinylbenzene-co-chloromethylstyrene)

To a 3 l three-necked flask equipped with a stirrer, a thermometer and acooling tube, there were introduced, at room temperature, 1500 g ofwater, 2.5 g of polyvinyl alcohol (available from The Nippon SynthemicalChemical Industry Co., Ltd. under the trade name of GOSENOL) and 80 g ofsodium chloride and they were sufficiently stirred to dissolve. To thesolution, there was added, at room temperature, a solution of 206 g ofchloromethylstyrene (available from Seimi Chemical Co., Ltd. under thetrade name of CMS-AM), 19.5 g of divinylbenzene, and 4.0 g of benzoylperoxide in 200 g of toluene and the solution was stirred for one hourat 110 rpm in a nitrogen gas stream. The temperature of the solution wasraised to 70° C. to perform the reaction for 7 hours, followed byfiltering off the resulting resin spheres, immersing the resin in 5 l ofwarm water of 50° C. to subject it to ultrasonic washing for 30 min. Theresin was likewise washed with 2 l of methanol, 2 l of acetone and 2 lof ethyl acetate, dried at 100° C. under a reduced pressure to obtain221.2 g of spherical resin particles having a particle size of not morethan 1 mm. The resin was subjected to elemental analysis to determinethe content of chlorine and it was confirmed that the content was5.89×10⁻³ mole/g resin.

Preparation of Poly(divinylbenzene-co-tributylammonio-methylstyrenechloride) (Compound 3)

20 g of poly(divinylbenzene-co-chloromethylstyrene) spherical particlesprepared above was weighed and put in a 500 ml 3-necked flask equippedwith a stirrer, a thermometer and a cooling tube followed by adding 40 gof isopropyl alcohol, 40 g of dimethylacetamide and 40 g oftributylamine and swelling the resin for 7 hours at room temperaturewith stirring. The resin was heated to 85° C. to react it for 8 hoursunder refluxing. Then, the reaction system was cooled to roomtemperature and solid contents (spherical resin particles) were filteredoff. The resin spheres were immersed in warm water of 50° C. to performultrasonic washing for 30 min., followed by repeating ultrasonic washingusing 2 l of methanol, 2 of acetone, 2 l of ethyl acetate and 2 l ofacetone in this order for every 20 min. and drying at 120° C. under areduced pressure to obtain 38.6 g of spherical resin particles. Thechloride ion content was 2.70×10⁻³ (mole/g resin).

The chloride ion content was determined by swelling the ground resin in1N sodium nitrate solution and titrating the solution with 0.1N silvernitrate.

PREPARATION EXAMPLE 2 Preparation ofN-vinylbenzyl-N,N,N-trihexylammonium chloride

54.9 g (0.36 mole) of chloromethylstyrene, 80.7 g (0.30 mole) oftri-n-hexylamine, 0.5 g of nitrobenzene as a polymerization inhibitorand 400 ml of acetonitrile were fed to 1 l 3-necked flask and they wererefluxed under heating for 7 hours with stirring.

After cooling to room temperature, the solution was washed with 500 mlof n-hexane several times to remove unreacted chloromethylstyrene. Thesolution was concentrated to precipitate crystals and the crystals wererecrystallized from 500 ml of ethyl acetate to obtain 103.89 g ofintended N-vinylbenzyl-N,N,N-trihexylammonium chloride as white crystals(yield: 82.1%). The molecular structure of the resultant compound wasconfirmed by ¹ H-NMR and elemental analysis.

Preparation of Poly(divinylbenzene-co-trihexylammoniomethylstyrenechloride) (Compound 4)

288 g of water and 143.5 g (0.34 mole) ofN-vinylbenzyl-N,N,N-trihexylammonium chloride were introduced into a 3 l3-necked flask equipped with a stirrer, a thermometer and a cooling tubeto let sufficiently absorb water to thus obtain an oily substance. Tothe oily substance, there were added 7.8 g (0.06 mole) of divinylbenzeneand 3.0 g of azobisisobutyronitrile (available from WACO JUNYAKU CO.,LTD. under the trade name of V-60) and the mixture was stirred todissolve. Further, a solution of 1080 g of calcium chloride and 2.3 g ofpolyvinyl alcohol (the same as that used above) in 1152 g of water wasadded to the resultant solution and the solution was stirred at roomtemperature for 30 min. at 135 rpm in a nitrogen gas stream. Thetemperature of the solution was raised to 70° C. and was stirred for 6hours.

The solution was cooled to room temperature, the solid contents werefiltered off and they were subjected to ultrasonic washing in 2 l ofdistilled water maintained at 50° C. for 30 min. Then, the ultrasonicwashing was repeated using 2 l of methanol, 2 l of acetone and 2 l ofethyl acetate as solvents and the solid was dried at 100° C. under areduced pressure to obtain 122.6 g of spherical particles. The chlorinecontent thereof was 1.8×10⁻³ (mole/g resin).

PREPARATION EXAMPLE 3 Preparation ofPoly(divinylbenzene-co-trihexylammoniomethylstyrenechloride-co-chloromethylstyrene)

There were introduced, into a 5 l 3-necked flask equipped with astirrer, a thermometer and a cooling tube, 360 g of water and 84.4 g(0.2 mole) of N-vinylbenzyl-N,N,N-trihexylammonium chloride to letsufficiently absorb water to thus obtain an oily substance. To the oilysubstance, there were added 10.4 g (0.08 mole) of divinylbenzene, 18.3 g(0.12 mole) of chloromethylstyrene (the same as that used above) and 2.9g of azobisisobutyronitrile (the same as that used above) and themixture was stirred to dissolve. To the solution, there was added asolution of 864 g of calcium chloride and 2.0 g of polyvinyl alcohol(the same as that used above) in 930 g of water followed by stirring themixture at room temperature, for 30 min. at 120 rpm in a nitrogen gasstream. The temperature of the solution was raised to 80° C. and thesolution was stirred for 7 hr.

The solution was cooled to room temperature followed by filtering offthe solid contents obtained and subjecting them to ultrasonic washing in2 l of distilled water maintained at 50° C. for 30 min. The ultrasonicwashing was repeated using 2 l each of methanol, acetone and ethylacetate as solvents and the solid contents were dried at 100° C. under areduced pressure to obtain 95.2 g of spherical particles. The resultantresin was analyzed by elemental analysis and it was found that the totalchlorine content thereof was 2.78×10⁻³ (mole/g resin). In addition, theresin was titrated to obtain chloride ion content and it was found to be1.65×10⁻³ (mole/g resin).

Preparation of Poly(divinylbenzene-co-tributylammoniomethylstyrenechloride-co-trihexylammoniamethylstyrene chloride) (Compound 51)

There was introduced 75 g of the spherical particles ofpoly(divinylbenzene-co-trihexylammoniomethylstyrenechloride-co-chloromethylstyrene) into an 1 l 3-necked flask providedwith a stirrer, a thermometer and a cooling tube and 100 ml of isopropylalcohol, 100 ml of acetonitrile and 150 g of tributylamine were addedthereto to swell the polymer at room temperature for 7 hr. withstirring. The solution was heated to 80° C. to cause a reaction for 9hr. with refluxing the solvent. Thereafter, the reaction system wascooled to room temperature and the resultant solid contents (sphericalresin particles) were filtered off. The spherical resin was immersed inwarm water of 50° C. to carry out ultrasonic washing for 30 min. and itwas repeated using 2 l each of methanol, acetone, ethyl acetate andacetone in this order.

PREPARATION EXAMPLE 5 Preparation ofPoly(divinylbenzene-co-chloromethylstyrene)

There were introduced, at room temperature, 3000 of water, 5.0 g ofpolyvinyl alcohol (available from The Nippon Synthemical ChemicalIndustry Co., Ltd. under the trade name of GOSENOL) and 160 g of sodiumchloride into a 5 l 3-necked flask equipped with a stirrer, athermometer and a cooling tube and the mixture was sufficiently stirredto dissolve. To the solution, there was added a solution of 412 g ofchloromethylstyrene (available from SEIMI Chemicals Co., Ltd. under thetrade name of CMS-AM), 43.4 g of divinylbenzene and 8.0 g of benzoylperoxide in 500 g of toluene at room temperature, followed by stirringthe solution for 30 min. at 120 rpm in a nitrogen gas stream, raisingthe temperature to 70° C. and reacting for 7 hr. After the reaction, theresulting spherical resin particles were filtered off, followed byimmersing them in 5 l of warm water of 50° C. to perform ultrasonicwashing for 30 min., likewise repeating the ultrasonic washing using 2 leach of methanol, acetone and ethyl acetate and drying at 100° C. undera reduced pressure to obtain 440 g of spherical resin particles having aparticle size of not more than 1 mm. The resin was subjected toelemental analysis and the chlorine content thereof was found to be5.85×10⁻³ mole/g resin.

Preparation of Poly(divinylbenzene-co-trimethylammoniomethylstyrenechloride-co-tributylammoniomethylstyrene chloride) (Compound 49)

20 g of poly(divinylbenzene-co-chloromethylstyrene) spherical particleswere introduced into a 500 ml 3-necked flask equipped with a stirrer, athermometer and a cooling tube, and 70 g of isopropyl alcohol, 30 g ofdimethylformamide and 40 g tributylamine were added thereto to swell theresin at room temperature for 30 min. with stirring. The reaction systemwas heated to 80° C. and the reaction was continued for 6 hr. withrefluxing the solvent. Then, the reaction system was cooled to roomtemperature, the resulting solid contents was filtered off, followed byadding 40 g of 30% aqueous trimethylamine solution, reacting at roomtemperature for 2 hr., raising the temperature to 80° C. by heating forone hour and filtering off the resin particles in the system. Thespherical resin was sufficiently washed with running warm water of 50°C., ultrasonic washing was performed for every 30 min. using 2 l each ofmethanol, acetone, ethyl acetate and acetone in this order and the resinwas dried at 120° C. under a reduced pressure to obtain 30.0 g ofspherical resin particles. The chloride ion content thereof was 3.1×10⁻³(mole/g resin).

The chloride ion content was determined by swelling the ground resin in1N sodium nitrate solution and titrating the solution with 0.1N silvernitrate.

PREPARATION EXAMPLE 6 Preparation ofPoly(divinylbenzene-co-trihexylammoniomethylstyrenechloride-co-chloromethylstyrene)

There were introduced, at room temperature, 360 g of water and 168.9 g(0.40 mole) of N-vinylbenzyl-N,N,N-trihexylammonium chloride to letsufficiently absorb water to thus obtain an oily substance. To the oilysubstance, there were added 5.2 g (0.04 mole) of divinylbenzene, 9.2 g(0.06 mole) of chloromethylstyrene and 4.0 g of benzoyl peroxide andfurther a solution of 1350 g of calcium chloride in 1,000 g of water anda solution of 2.9 g of polyvinyl alcohol (the same as that used above)in 440 g of water with stirring. The solution was stirred at roomtemperature, at 150 rpm in a nitrogen gas stream for 30 min., thenheated to 70° C. and further stirred for 6 hr.

The solution was cooled down to room temperature, the resulting solidcontents were filtered off and were subjected to ultrasonic washing for30 min. in 2 l of distilled water maintained at 50° C. Then, the washingwas repeated using, as solvents, 2 l each of methanol, acetone and ethylacetate and the solid was dried at 100° C. under a reduced pressure toobtain 176.8 g of spherical resin particles (chloride ion content:2.1×10⁻³ mole/g resin).

Preparation of Poly(divinylbenzene-co-trimethylammoniomethylstyrenechloride-co-trihexylammoniomethylstyrene) (Compound 48)

150 g of thepoly(divinylbenzene-co-trihexylammoniomethylchloride-co-chloromethylstyrene)obtained above was introduced into a 2 l 3-necked flask equipped with astirrer, a thermometer and a cooling tube and 300 ml of dichloroethanewas added thereto at room temperature to swell the resin for 30 min.Then, 500 ml of 30% aqueous trimethylamine solution was added, followedby allowing to stand for one hour to swell and reacting at roomtemperature for 2 hr. with stirring. Thereafter, the system was heatedto 80° C. to get out dichloroethane from the system by azeotropy. 500 mlof water was added in three portions during heating to prevent drying ofthe resin. After continuing the removal of the solvent untildichloroethane was not distilled by azeotropy, the resultant solidcontents were filtered off and washed with running water sufficiently.Then, the solid was subjected to ultrasonic washing in 3 l of warm waterof 50° C. for 30 min., followed by repeating the washing using 2 l eachof methanol, acetone, ethyl acetate and acetone for every 30 min. anddrying the solid at 120° C. under a reduced pressure to obtain 147.2 gof spherical resin particles. The chloride ion content thereof was3.0×10⁻³ (mole/g).

In the general formula (VIII), G preferably represents ##STR18## fromthe viewpoint of selective removal of iodide ions and more preferably Grepresents such a functional group wherein the total carbon atom numberof R₁₄ to R₁₆ is not less than 12. Specifically, preferred are Compounds(3) to (5), (12), (19), (20), (23), (24), (28), (29), (32), and (44) to(49).

In the method of this invention, the bleaching process is performedwhile a part or whole of a bleaching solution is brought into contactwith an anion-exchange resin. The contact between the bleaching solutionand the anion-exchange resin can be carried out by, for instance,packing an anion-exchange resin in a column and incorporating it into acirculating pump of a bleaching bath (e.g., a bleaching or bleach-fixingbath); or charging it into a subtank separately disposed andcontinuously or intermittently circulating a bleaching solution from thebleaching bath to the subtank. Alternatively, the contact can beperformed by a method comprising packaging an anion-exchange resin in abag of fine mesh net and immersing the same in the bath for bleaching.

The amount of the bleaching solution to be brought into contact with theanion-exchange resins is preferably not less than one liter, morepreferably 5 to 3000 liters and most preferably 15 to 2000 liters perliter of the anion-exchange resin.

The terms "amount of the processing solution per liter of theanion-exchange resin" herein means the amount of the processing solutionsupplemented during a continuous processing of light-sensitive materialsper liter of the resin and if a replenisher is supplemented in theamount defined above, the resin should be replaced with a fresh one.

The method may be a continuous or batchwise one, preferably a continuousmethod.

The continuous processing herein means a processing in which aprocessing solution is supplemented while the processing is continuouslyor intermittently performed for a long time period. The amount of theprocessing solution (replenisher) is determined depending on, forinstance, area of the light-sensitive materials to be processed andprocessing time.

In addition, the method can be applied to a so-called regenerationsystem in which a solution obtained by bringing the overflow (bleachingsolution) from a bleaching bath into contact with an anion-exchangeresin is reused as a replenisher.

In general, supplementation of the fixing and bleach-fixing solutions isperformed depending on area of the light-sensitive materials to beprocessed, but if the amount of the replenisher is saved, the rate ofbleaching is lowered because of the accumulation of substances dissolvedout from the light-sensitive material, as a result, the rate ofdesilvering is lowered and if the processing time is constant,insufficient bleaching, i.e., insufficient desilvering is caused.

However, in the method of this invention, such delay in bleaching can beprevented since the foregoing bleaching accelerators are used and areplenisher-saved and rapid processing can be achieved.

The light-sensitive materials to be processed by the method of thisinvention includes emulsion layers containing the aforesaid silveriodide. Other constructions thereof will be described below.

Treatment of Emulsion Layer and General Additives

The emulsions as used herein are subjected to physical and/or chemicalripening and are spectrally sensitized. Additives used in such processesare disclosed in Research Disclosure (RD), Vol. 176, No. 17643(December, 1978) and ibid, Vol. 187, No. 18716 (November, 1979). Therelevant passages are summarized in the following Table. Photographicadditives usable in the invention are also disclosed in the samearticles (two Research Disclosures) and likewise the relevant passagesare listed in the following Table.

    ______________________________________                                        Kind of Additive   RD 17643  RD 18716                                         ______________________________________                                        1.   Cemical Sensitizer                                                                              p. 23     p. 648, right                                                                 column                                       2.   Sensitivity Enhancing Agent p. 648, right                                                                 column                                       3.   Spectral Sensitizing Agent                                                                      p. 23-24  infra p. 648,                                                                 right column                                 4.   Supersensitizing Agent      p. 649, right                                                                 column                                       5.   Brightener        p. 24                                                  6.   Antifoggant & Stabilizer                                                                        p. 24-25  p. 649, right                                                                 column                                       7.   Coupler           p. 25                                                  8.   Organic Solvent    "                                                     9.   Light Absorber & Filter Dye                                                                     p. 25-26  p. 649, right                                     and Ultraviolet Absorber    to p. 650 left                                                                column                                       10.  Stain Resistant Agent                                                                           p. 25, right                                                                            p. 650, left                                                        column    to right column                              11.  Dye Image Stabilizer                                                                            p. 25                                                  12.  Film Hardening Agent                                                                            p. 26     p. 651, left                                                                  column                                       13.  Binder            p. 26     p. 651, left                                                                  column                                       14.  Plasticizer & Lubricant                                                                         p. 27     p. 650, right                                                                 column                                       15.  Coating Aid & Surfactant                                                                        p. 26-27  p. 650, right                                                                 column                                       16.  Antistatic Agent  p. 27     p. 650, right                                                                 column                                       ______________________________________                                    

Color Couplers

The color light-sensitive materials to be processed in the presentinvention may contain color couplers. "Color coupler(s)" herein means acompound capable of forming a dye through coupling reaction with anoxidized form of an aromatic primary amine developing agent. Typicalexamples of useful color couplers are naphthol or phenol type compounds,pyrazolone or pyrazoloazole type compounds, and linear or heterocyclicketomethylene compounds. Cyan, magenta and yellow color couplers whichmay be used in the present invention are disclosed in the patents citedin Research Disclosure No. 17643 (December, 1978) VII-D; and ibid, No.18717 (November, 1979).

The color couplers to be incorporated into the light-sensitive materialsare preferably made non-diffusible by imparting thereto ballast groupsor polymerizing them. 2-Equivalent couplers which are substituted withelimination groups are more preferable than 4-equivalent couplers inwhich a hydrogen atom is in a coupling active site, because the amountof coated silver can be decreased. Furthermore, couplers in which aformed dye has a proper diffusibility, non-color couplers, DIR couplerswhich release a development inhibitor through coupling reaction orcouplers which release a development accelerator during couplingreaction may also be used.

Magenta couplers usable in the invention include couplers of an oilprotect type of indazolone, cyanoacetyl, or preferably pyrazoloazoletype ones such as 5-pyrazolones and pyrazolotriazoles. Among5-pyrazolone type couplers, couplers whose 3-position is substitutedwith an arylamino or acylamino group are preferred from the viewpoint ofcolor phase and color density of the formed dye. Typical examplesthereof are disclosed in U.S. Pat. Nos. 2,311,082; 2,343,703; 2,600,788;2,908,573; 3,062,653; 3,152,896 and 3,936,015. An elimination group ofthe 2-equivalent 5-pyrazolone type couplers is preferably a nitrogenatom elimination group described in U.S. Pat. No. 4,310,619 and anarylthio group described in U.S. Pat. No. 4,351,897. The 5-pyrazolonecouplers having ballast groups such as those described in EuropeanPatent No. 73,636 provide high color density.

As examples of pyrazoloazole type couplers, there may be mentioned suchpyrazolobenzimidazoles as those disclosed in U.S. Pat. No. 3,369,879,preferably such pyrazolo(5,1-c)(1,2,4)triazoles as those disclosed inU.S. Pat. No. 3,725,067, such pyrazolotetrazoles as those disclosed inResearch Disclosure No. 24220 (June, 1984) and such pyrazolopyrazoles asthose disclosed in Research Disclosure No. 24230 (June, 1984).Imidazo(1,2-b)pyrazole disclosed in European Patent No. 119,741 ispreferred on account of small yellow minor absorption of formed dye andlight fastness. Pyrazolo(1,5-b)(1,2,4)triazole described in EuropeanPatent No. 119,860 is particularly preferred. In particular in thepresent invention, the use of pyrazoloazole and 2-equivalent pyrazolonetype magenta couplers represented by the following general formulas (M)and (m) is most preferable from the viewpoint of substantiallypreventing an increase in magenta stains during continuous processingand enhancing desilvering properties: ##STR19## Wherein Za and Zbrepresent --CH═, ##STR20## or ═N--; R₁ and R₂ represent a hydrogen atomor a substituent; X represents a hydrogen atom or a group capable ofbeing eliminated through the coupling reaction with an oxidized form ofan aromatic primary amine developing agent. If Za=Zb is a carbon-carbondouble bond, it encloses cases where Za=Zb is a part of the aromaticring.

Among the pyrazoloazole magenta couplers of formula (M), preferred arethose represented by the following general formulas (M-2) to (M-6):##STR21##

In the general formulas (M-2) to (M-6), R₁ and X are the same as thosein formula (M), R₂₁ and R₂₂ have the same meanings as those of R₂defined above in connection with formula (M) and l is an integer of 1 to4.

The pyrazoloazole magenta couplers represented by formulas (M-2) to(M-6) will be explained in more detail below.

R₁, R₂₁ and R₂₂ each represents a hydrogen atom, a halogen atom (such asfluorine or chlorine atom), an alkyl group (such as methyl, ethyl,isopropyl, 1-butyl, t-butyl or 1-octyl), an aryl group (such as phenyl,p-tolyl, 4-nitrophenyl, 4-ethoxyphenyl,2-(2-octyloxy-5-t-octylbenzenesulfonamido) phenyl,3-dodecanesulfonamidophenyl or 1-naphthyl), a heterocyclic group (suchas 4-pyridyl or 2-furyl), a hydroxyl, an alkoxy (such as methoxy,ethoxy, 1-butoxy, 2-phenoxyethoxy or 2-(2,4-di-t-amylphenoxy)ethoxy), anaryloxy (such as phenoxy, 2-methoxyphenoxy, 4-methoxyphenoxy,4-nitrophenoxy, 3-butanesulfonamidophenoxy, 2,5-di-t-amylphenoxy or2-naphthoxy), a heterocyclic oxy (such as 2-furyloxy), an acyloxy (suchas acetoxy, pivaloyloxy, benzoyloxy or dodecoanoyloxy), analkoxycarbonyloxy (such as ethoxycarbonyloxy, t-butoxycarbonyloxy or2-ethyl-1-hexyloxycarbonyloxy), an aryloxycarbonyloxy (such asphenoxycarbonyloxy), a carbamoyloxy (such as N,N-dimethylcarbamoyloxy orN-butylcarbamoyloxy), a sulfamoyloxy (such as N,N-diethylsulfamoyloxy orN-propylsulfamoyloxy), a sulfonyloxy (such as methanesulfonyloxy orbenzenesulfonyloxy), a carboxyl, an acyl (such as acetyl, pivaloyl, orbenzoyl), an alkoxycarbonyl (such as ethoxycarbonyl), an aryloxycarbonyl(such as phenoxycarbonyl), a carbamoyl (N,N-dibutylcarbamoyl,N-ethyl-N-octylcarbamoyl or N-propylcarbamoyl), an amino (such as amino,N-methylamino or N,N-dioctylamino), an anilino (such asN-methylanilino), a heterocyclic amino (such as 4-pyridyl amino), anamido (such as acetamido or benzamido), an urethane (such asN-hexylurethane or N,N-dibutylurethane), an ureido (such asN,N-dimethylureido or N-phenylureido), a sulfonamido (such asbutanesulfonamido or p-toluenesulfonamido), an alkylthio (such asethylthio or octylthio), an arylthio (such as phenylthio or4-dodecylphenylthio), a heterocyclic thio (such as 2-benzothiazolylthioor 5-tetrazolylthio), a sulfinyl (such as benzenesulfinyl), a sulfonyl(such as methanesulfonyl, octanesulfonyl or p-toluenesulfonyl), a sulfo,a cyano or a nitro group.

X represents a hydrogen, a halogen (such as fluorine, chlorine orbromine atom), a carboxyl, a group bonded through an oxygen atom (suchas acetoxy, benzoyloxy, phenoxy, 4-cyanophenoxy, tolyloxy,4-methanesulfonylphenoxy, 4-ethoxycarbonylphenoxy, 2-naphthoxyethoxy,2-cyanoethoxy or 2-benzothiazolyloxy), a group bonded through a nitrogenatom (such as benzenesulfonamido, heptafluorobutanamido,pentafluorobenzamido, octanesulfonamido, p-cyanophenylureido,1-piperidinyl, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl,1-benzyl-5-ethoxy-3-hydantoinyl, 1-imidazolyl, 1-pyrozolyl,3-chloro-1-pyrazolyl, 3,5-dimethyl-1,2,4-triazol-1-yl or 5- or6-bromobenzotriazol-1-yl), or a group bonded through a sulfur atom (suchas phenylthio, 2-butoxy-5-t-octylphenyl, 4-methanesulfonylphenylthio,4-dodecyloxyphenylthio, 2-cyanoethylthio, 1-ethoxycarbonyltridecylthio,2-benzothiazolylthio, or 1-phenyl-1,2,3,4-tetrazole-5-thio).

Among the pyrazoloazole magenta couplers represented by formulas (M-2)to (M-6), preferred are those of formulas (M-3) and (M-4).

Typical examples of the pyrazoloazole magenta couplers of formulas (M-2)to (M-6) are as follows, but the present invention is not restricted tothese specific examples. ##STR22##

In the formula, Ar represents a substituted or unsubstituted phenylgroup, Y is a group which is eliminated through a coupling reaction withan oxidized form of an aromatic primary amine color developing agent toform a dye. V represents a halogen atom or an alkoxy or alkyl group, Rrepresents a group capable of being substituted on the benzene ring, ann is 1 or 2. When n is 2, two groups R may be the same or different.

The magenta couplers represented by formula (m) used in the inventionwill be explained in detail below.

First of all, each group Ar, Y, V or R in formula (m) will bespecifically explained below.

Ar: This represents a phenyl group, in particular, a substituted phenylgroup. Examples of such substituents are halogen atoms, alkyl groups,alkoxy groups, aryloxy groups, alkoxycarbonyl groups, cyano group,carbamoyl group, sulfamoyl group, sulfonyl group, sulfonamido groups,acylamino group. The phenyl group represented by Ar may have two or moresubstituents. Particularly preferred are halogen atoms and mostpreferred is chlorine atom(s).

Y: This represents a group which is eliminated when the coupler causescoupling with an oxidized form of an aromatic primary amine colordeveloping agent to form a dye.

Specific examples thereof are halogen atoms, alkoxy, aryloxy, acyloxy,arylthio, alkylthio groups and ##STR23## (wherein Z represents a grouphaving an atom selected from oxygen, nitrogen and sulfur atoms requiredfor forming a 5- or 6-membered ring together with the nitrogen atom).Examples of -N Z are pyrazolyl, imidazolyl, triazolyl and tetrazolylgroups. Particularly preferred Y are those eliminated at sulfur atom.

V represents a halogen atom or an alkoxy or alkyl group. Preferred arehalogen atoms, in particular a chlorine atom.

R: represents a group capable of being substituted on the benzene ringand examples thereof include halogen atoms, R'--, R'O--, R'--CO--NR"--,R'SO₂ --NR"--, R"--O--CO--NR", R'--COO--, R'--NR"--CO--, R'--NR"--SO₂--, R'--O--CO--, R'--NR"--CO--NR"'-- and ##STR24## Wherein R', R", R"'may be the same or different and each represents a hydrogen atom or asubstituted or unsubstituted alkyl, alkenyl or aryl group. Among these,preferred are R'--CONH--, R'SO₂ NH-- and ##STR25##

Specific examples of the magenta couplers used in the inventionrepresented by formula (m) will be listed below, but the invention isnot restricted to these specific examples. ##STR26##

The couplers represented by formula (m) as used in the present inventionare farther detailed in J.P. KOKAI Nos. 60-262161 (pp. 3-7) and60-238832 (pp. 6-7) and specific examples thereof usable in theinvention are disclosed in J.P. KOKAI Nos. 60-262161 (pp. 7-11) and60-238832 (pp. 7-9).

The magenta couplers used in the invention can be prepared by methodsdisclosed in, for instance, J.P. KOKOKU No. 53-34044; J.P. KOKAI No.55-62454 and U.S. Pat. No. 3,701,783.

Cyan couplers which may be used in the present invention includenaphthol or phenol type couplers of an oil protect type. Typicalnaphthol type couplers are disclosed in U.S. Pat. No. 2,474,293. Typicalpreferred 2-equivalent naphtholic couplers of oxygen atom eliminationtype are disclosed in U.S. Pat. Nos. 4,052,212; 4,146,396; 4,228,233;and 4,296,200. Exemplary phenol type couplers are disclosed in U.S. Pat.Nos. 2,369,929; 2,801,171; 2,772,162 and 2,895,826. Cyan couplers whichare resistant to humidity and heat are preferably used in the presentinvention. Examples thereof are phenol type cyan couplers having analkyl group having not less than two carbon atoms at a metha-position ofa phenolic nucleus as disclosed in U.S. Pat. No. 3,772,002;2,5-diacylamino substituted phenol type couplers as disclosed in U.S.Pat. Nos. 2,772,162; 3,758,308; 4,126,396; 4,334,011 and 4,327,173; DEOSNo. 3,329,729; and Japanese Patent Application Serial (hereunderreferred to as "J.P.A.") No. 58-42671; and phenolic couplers having aphenylureido group at the 2-position and an acylamino group at the5-position as disclosed in U.S. Pat. Nos. 3,446,622; 4,333,999;4,451,559 and 4,427,767.

A typical yellow coupler usable in the present invention is anacylacetamide coupler of an oil protect type. Examples thereof aredisclosed in U.S. Pat. Nos. 2,407,210; 2,875,057; and 3,265,506.2-Equivalent yellow couplers are preferably used in the presentinvention. Typical examples thereof include the yellow couplers of anoxygen atom elimination type disclosed in U.S. Pat. Nos. 3,408,194;3,447,928; 3,933,501 and 4,022,620, or the yellow couplers of a nitrogenatom elimination type disclosed in J.P. KOKOKU No. 55-10739; U.S. Pat.Nos. 4,401,752; and 4,326,024, Research Disclosure No. 18053 (April,1979), U.K. Patent No. 1,425,020, DEOS Nos. 2,219,917; 2,261,361;2,329,587 and 2,433,812. α-Pivaloyl acetanilide type couplers areexcellent in fastness, particularly light fastness, of the formed dye.α-Benzoyl acetanilide type couplers yield high color density.

Graininess may be improved by using together a coupler which can form adye being moderately diffusible. As such dye-diffusing couplers, somemagenta couplers are specifically described in U.S. Pat. No. 4,366,237and U.K. Patent No. 2,125,570 and some yellow, magenta and cyan couplersare specfically described in European Patent No. 96,570 and DEOS No.3,234,533.

Dye-forming couplers and the aforesaid special couplers may be a dimeror a higher polymer. Typical examples of polymerized dye-formingcouplers are described in U.S. Pat. Nos. 3,415,820 and 4,080,211.Examples of polymerized magenta couplers are described in U.K. PatentNo. 2,102,173 and U.S. Pat. No. 4,367,282.

In order to meet properties required for light-sensitive materials, twoor more couplers may be used together in a single light-sensitive layer,or the same coupler may be introduced in two or more differentlight-sensitive layers.

The standard amount of the colored couplers to be used is 0.001 to 1mole and preferred amount thereof is 0.01 to 0.5 mole for yellowcouplers, 0.003 to 0.3 mole for magenta couplers and 0.002 to 0.3 molefor cyan couplers per mole of light-sensitive silver halide.

The couplers used in the invention can be introduced, into the colorlight-sensitive materials, by a variety of known methods for dispersion.Examples of high boiling point organic solvents used in the oil-in-waterdispersion method are disclosed in U.S. Pat. No. 2,322,027. Specificexamples of processes, effects and latexes for impregnation, for latexdispersion method are, for instance, disclosed in U.S. Pat. No.4,199,363 and DE OLS Nos. 2,541,274 and 2,541,230.

Substrate

The photographic light-sensitive materials to be processed by thepresent invention are applied to the surface of a flexible substratesuch as a plastic film (e.g., cellulose nitrate, cellulose acetate orpolyethylene terephthalate) or paper; or a rigid substrate such as aglass plate. Substrates and methods for applying the photographiclight-sensitive materials thereto are detailed in Research Disclosure,Vol. 176, No. 17643, Item XV (p. 27) and XVII (p. 28) (December, 1978).

Typical examples of the photographic light-sensitive materials to beprocessed by the method of the present invention include color negativefilms for general use or motion picture, color reversal films for slideor television, color paper, color positive films, color reversal paperand color direct positive light-sensitive materials.

Development Processing

The processing method of this invention is particularly characterized inthat the amount of a processing solution having fixing ability to besupplemented is preferably restricted to not more than 3,000 ml, morepreferably 30 to 2,000 ml and in particular 45 to 1,000 ml. The term "abath having fixing ability" herein means a fixing solution andbleach-fixing solution and thus the amount of these solutionsreplenished is limited to the range defined above.

The method of this invention comprises a variety of combination of theprocessing processes and specific examples thereof are as follows:

(i) Development-Bleach-fixing-Water Washing-Drying

(ii) Development-Bleach-fixing-Stabilization-Drying

(iii) Development-Bleach-fixing-Water Washing-Stabilization-Drying

(iv) Development-Bleaching-Bleach-fixing-Water Washing-Drying

(v) Development-Bleaching-Bleach-fixing-WaterWashing-Stabilization-Drying

(vi) Development-Bleaching-Bleach-fixing-Stabilization-Drying

In this respect, it is also possible in the foregoing processes, tocarry out water washing process between the development and bleaching orbleach-fixing processes; or between the bleaching and fixing processes.Each processing may be performed according to any manners such as asingle bath processing, a multistage countercurrent system or multistagedirect flow system.

The processing time of the bleaching process of the present invention ispreferably not more than 10 minutes and in particular if it ranges from1 to 5 minutes, the marked enhancement of bleaching properties(desilvering properties) and stain increment-inhibiting effect can beachieved and thus the objects of this invention can effectively beattained.

Development

The color developer used to develop light-sensitive materials ispreferably an aqueous alkaline solution containing, as a principalcomponent, an aromatic primary amine type color developing agent.Although aminophenol type developing agents are also useful as the colordeveloping agent, but preferred are p-phenylenediamine type compoundswhose typical examples are 3-methyl-4-amino-N,N-diethylaniline,3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,3-methyl-4-amino-N-ethyl-N-β-methanesulfonamido-ethylaniline, and3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and sulfates,hydrochlorides or p-toluenesulfonates thereof. These diamines in theform of salts are in general more stable than those in the free stateand, therefore, they are preferably used in the form of salts.

The color developer in general contains, in addition to the foregoingcomponents, pH buffering agents such as carbonates, borates orphosphates of alkali metals; development inhibitors such as bromides,iodides, benzimidazoles, benzothiazoles or mercapto compounds; orantifoggants. The color developer may optionally comprise various kindsof preservatives such as hydroxylamine, diethylhydroxylamine, sulfitesand compounds disclosed in J.P.A. No. 61-280792; organic solvents suchas triethanolamine and diethylene glycol; development accelerators suchas benzyl alcohol, polyethylene glycol, quaternary ammonium salts andamines; fogging agents such as dye-forming couplers, competing couplersand sodium borohydride; auxiliary developing agents such as1-phenyl-3-pyrazolidone; thickening agents; a variety of chelatingagents such as aminopolycarboxylic acid, aminopolyphosphonic acid,alkylphosphonic acid and phosphonocarboxylic acid; and anti-oxidizingagents as disclosed in DE OLS No. 2,622,950.

In addition, if the reversal processing is performed, the photographiclight-sensitive materials are in general subjected to monochromaticdevelopment prior to the color development. In such a monochromaticdeveloper, there may be used any known monochromatic developing agents,for instance, dihydroxybenzenes such as hydroquinone; 3-pyrazolidonessuch as 1-phenyl-3-pyrazolidone; and aminophenols such asN-methyl-p-aminophenol, which may be used alone or in combination.

The amount of the color developer and the monochromatic developer to bereplenished generally varies depending on the kinds of thelight-sensitive materials to be processed and it is in general not morethan 3 liters per 1 m² of the light-sensitive material to be processed.However, it can be reduced to not more than 500 ml by reducing theamount of bromide ions present in the replenisher. Upon reducing theamount of the replenisher, the area of the opening of the processingbath should be limited to a small value to prevent the evaporation ofthe solution and the oxidation thereof with air. Alternatively, theamount of the replenisher may further be reduced by utilizing a meansfor suppressing the accommodation of bromide ions in the developer.

Bleaching, Fixing

Subsequently, the color developed photographic emulsion layer isgenerally processed with a bleach-fixing solution. Moreover, afterbleaching, a bleach-fixing treatment may be carried out to speed up theprocessing. Further, it is also possible to perform fixing treatmentprior to bleach-fixing treatment or to perform bleaching treatment afterbleach-fixing treatment, depending on purposes. As the bleaching agents,there may be used, for instance, compounds of polyvalent metals such asiron(III), cobalt(III), chromium(IV) and copper(II); peracids; andquinones. Typical examples thereof include ferricyanides; bichromates;organic complexes of iron(III) or cobalt(III); aminopolycarboxylic acidssuch as ethylenediaminetetraacetic acid, diethylenetriaminepentaaceticacid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,1,3-diaminopropanetetraacetic acid and glycol ether diaminetetraaceticacid; complexes of organic acids such as citric acid, tartaric acid ormalic acid; persulfates; hydrobromides; manganates; and nitrosophenol.Among these, ferric aminopolycarboxylates such as ferricethylenediaminetetraacetate and persulfates are preferably used onaccount of rapid processing and prevention of environmental pollution.

Examples of fixing agents are thiosulfates, thiocyanates, thioether typecompounds, thioureas and a large amount of iodides, but in generalthiosulfates are used and particularly ammonium thiosulfate is mostwidely used. Preferred preservatives for the bleach-fixing solution andthe fixing solution are sulfites, bisulfites and carbonylbisulfiteadducts.

Water Washing and Stabilization

It is common that the silver halide color photographic light-sensitivematerials to be processed by the present invention are subjected towater washing and/or stabilization processes after the desilveringprocess.

The amount of washing water in water washing process can widely beestablished depending on a variety of conditions such as characteristicsof the light-sensitive materials to be processed (for instance,materials used such as couplers), applications, the temperature of thewashing water, the number of washing tanks (step number), and themanners of the replenishment, for instance, direct flow system andcountercurrent flow system. Among these, the relation between the amountof water and the number of water washing tanks in the multistagecountercurrent flow system can be obtained by the method disclosed inJournal of the Society of Motion Picture and Television Engineers, 1955,May, Vol. 64, p. 248-253.

Although, the multistage countercurrent flow system disclosed in theforegoing article makes it possible to extremely reduce the amount ofwashing water, the retention time of water in the tanks increases and asa result bacteria proliferates therein which leads to the formation offloating substances and the adhesion of the substances to the processedlight-sensitive materials.

In order to solve such problems, a method for reducing the amount ofcalcium and magnesium, in the processing of the color light-sensitivematerials, disclosed in J.P.A. No. 61-131632 can be effectively adoptedin the invention. Alternatively, the problems can also be solved byutilizing isothiazolone compounds and thiabendazoles disclosed in J.P.KOKAI No. 57-8542; such chlorine type antibacterial agents as sodiumchlorinated isocyanurates; benzotriazoles; or other antibacterial agentsdisclosed in "BOKIN BOBAIZAI NO KAGAKU (Chemistry of Antibacterial andAntifungus Agents)", Hiroshi HORIGUCHI; "BISEIBUTSU NO MEKKIN, SAKKINAND BOBAI GIJUTSU (Sterilization, Pasteurization and Mold ControllingTechniques)", edited by Sanitary Engineering Society; and "Dictionary ofAntibacterial and Antifungus Agents", edited by Japan Bacteria and FungiControlling Society.

In the present invention, the pH value of the washing water is 4 to 9and preferably 5 to 8. The temperature and time of the water washingprocess may vary depending on, for instance, the properties andapplications of the color light-sensitive materials to be processed, butin general the water washing is performed at a temperature of 15° to 45°C. for 20 seconds to 10 minutes and preferably 25° to 40° C. for 30seconds to 5 minutes.

In the invention, the color light-sensitive materials are directlyprocessed with a stabilization solution instead of the water washingprocess. In such a stabilization process, any known methods disclosed inJ.P. KOKAI Nos. 57-8543, 58-14834 and 60-220345 can be employed.

Additionally, the stabilization process may be carried out subsequent tothe water washing process and examples thereof are stabilization bathscontaining formalin and a surfactant, which is used as the final bathfor processing color light-sensitive materials for taking photographs.The stabilization solution may contain a variety of chelating agentsand/or antifungus agents.

The overflows associated with the supplementation of a replenisher tothe water washing and/or stabilization processes may be introduced intoother baths such as those for the desilvering process to reuse them.

The silver halide color light-sensitive materials processed by theinvention may contain a color developing agent for simplification ofprocesses and rapid processing. For that purpose, it is preferable touse a variety of precursors of the color developing agents. Examplesthereof include indoaniline compounds as disclosed in U.S. Pat. No.3,342,597; Schiff base type compounds as disclosed in U.S. Pat. No.3,342,599 and Research Disclosure Nos. 14850 and 15159; aldol compoundsas disclosed in Research Disclosure No. 13924; metal complex salts asdisclosed in U.S. Pat. No. 3,719,492; and urethane type compounds asdisclosed in J.P. KOKAI No. 53-135628.

For the purpose of promoting the color development, the silver halidecolor light-sensitive materials processed by the invention mayoptionally comprise various 1-phenyl-3-pyrazolidones. Typical examplesof such compounds are disclosed in, for instance, J.P. KOKAI Nos.56-64339; 57-144547 and 58-115438.

In the present invention, each processing solution is used at atemperature of 10° to 50° C. It generally ranges from 33° to 38° C., buthigher temperature may be used to promote the processing and to thusreduce the processing time, or a lower temperature may also be used toimprove the quality of images or the stability of the processingsolution. Moreover, to save the amount of silver in the colorlight-sensitive materials, processings utilizing a cobalt intensifier orhydrogen peroxide intensifier disclosed in German Patent No. 2,226,770and U.S. Pat. No. 3,674,499 can be employed.

Each processing bath may be provided with a heater, a temperaturesensor, a level sensor, a circulation pump, a filter, a floating cover,a squeezy and the like according to need.

Moreover, if a continuous processing is performed, the composition ofeach processing solution should be maintained by adding a replenisherfor each processing solution to achieve uniform finishing of theprocessed materials. The amount of the replenisher can be reduced tohalf or less of the standard replenished amount for cutting the cost andso on.

EXAMPLE

The present invention will hereunder be explained in more detail withreference to the following Examples, but the present invention is notrestricted to these specific Examples.

EXAMPLE 1

A multi-layered color light-sensitive material (Sample 101) was preparedby applying in order coating solutions having the following compositionson the surface of a substrate of cellulose triacetate ot which anunderlying layer had been applied.

Composition of the Light-sensitive Layer

In the following composition, the coated amounts are expressed in g/m²of elemental silver for silver halide and colloidal silver; in g/m² forcouplers, additives and gelatin; and in moles per mole of silver halideincluded in the same layer for sensitizing dyes.

    ______________________________________                                        1st Layer: Halation Inhibiting Layer                                          Black colloidal silver     0.2                                                Gelatin                    1.3                                                Coupler C-1                0.06                                               Ultraviolet absorber UV-1  0.1                                                Ultraviolet absorber UV-2  0.2                                                Dispersion oil Oil-1       0.01                                               Dispersion oil Oil-2       0.01                                               ______________________________________                                        2nd Layer: Intermediate Layer                                                 Fine grain silver bromide (average grain                                                                 0.15                                               size = 0.07μ)                                                              Gelatin                    1.0                                                Coupler C-2                0.02                                               Dispersion oil Oil-1       0.1                                                ______________________________________                                        3rd Layer: First Red-sensitive Emulsion Layer                                 Silver iodobromide emulsion (AgI = 2 mole %;                                                             0.4 (Ag)                                           diameter/thickness ratio = 2.5; average grain                                 size = 0.3μ; AgI content is high at the                                    inner portion)                                                                Gelatin                    0.6                                                Sensitizing dye I          1.0 × 10.sup.-4                              Sensitizing dye II         3.0 × 10.sup.-4                              Sensitizing dye III          1 × 10.sup.-5                              Coupler C-3                0.06                                               Coupler C-4                0.06                                               Coupler C-8                0.04                                               Coupler C-2                0.03                                               Dispersion oil Oil-1       0.03                                               Dispersion oil Oil-3       0.012                                              ______________________________________                                        4th Layer: Second Red-sensitive Emulsion Layer                                Silver iodobromide emulsion (AgI = 5 mole %;                                                             0.7 (Ag)                                           diameter/thickness ratio = 4.0; average grain                                 size = 0.7μ; AgI content is high at the                                    inner portion)                                                                Gelatin                    1.0                                                Sensitizing dye I          1 × 10.sup.-4                                Sensitizing dye II         3 × 10.sup.-4                                Sensitizing dye III        1 × 10.sup.-5                                Coupler C-3                0.24                                               Coupler C-4                0.24                                               Coupler C-8                0.04                                               Coupler C-2                0.04                                               Dispersion oil Oil-1       0.15                                               Dispersion oil Oil-3       0.02                                               ______________________________________                                        5th Layer: Third Red-sensitive Emulsion Layer                                 Silver iodobromide emulsion (AgI = 10 mole %;                                                            1.0 (Ag)                                           diameter/thickness ratio = 1.3; average grain                                 size = 0.8μ; AgI content is high at the                                    inner portion)                                                                Gelatin                    1.0                                                Sensitizing dye I          1 × 10.sup.-4                                Sensitizing dye II         3 × 10.sup.-4                                Sensitizing dye III        1 × 10.sup.-5                                Coupler C-6                0.05                                               Coupler C-7                0.1                                                Dispersion oil Oil-1       0.01                                               Dispersion oil Oil-2       0.05                                               ______________________________________                                        6th Layer: Intermediate Layer                                                 Gelatin                    1.0                                                Compound Cpd-A             0.03                                               Dispersion oil Oil-1       0.05                                               ______________________________________                                        7th Layer: First Green-sensitive Emulsion Layer                               Silver iodobromide emulsion (AgI = 2 mole %;                                                             0.3 (Ag)                                           diameter/thickness ratio = 2.5; average grain                                 size = 0.3μ; AgI content is high at the                                    inner portion)                                                                Gelatin                    1.0                                                Sensitizing dye IV           5 × 10.sup.-4                              Sensitizing dye VI         0.3 × 10.sup.-4                              Sensitizing dye V            2 × 10.sup.-4                              Coupler C-9                0.2                                                Coupler C-5                0.03                                               Coupler C-1                0.03                                               Compound Cpd-C             0.012                                              Dispersion oil Oil-1       0.5                                                ______________________________________                                        8th Layer: Second Green-sensitive Emulsion Layer                              Silver iodobromide emulsion (AgI = 4 mole %;                                                             0.4 (Ag)                                           diameter/thickness ratio = 4.0; average grain                                 size = 0.6μ; AgI content is high at the                                    inner portion)                                                                Gelatin                    1.0                                                Sensitizing dye IV           5 × 10.sup.-4                              Sensitizing dye V            2 × 10.sup.-4                              Sensitizing dye VI         0.3 × 10.sup.-4                              Coupler C-9                0.25                                               Coupler C-1                0.03                                               Coupler C-10               0.015                                              Coupler C-5                0.01                                               Compound Cpd-C             0.012                                              Dispersion oil Oil-1       0.2                                                ______________________________________                                        9th layer: Third Green-sensitive Emulsion Layer                               Silver iodobromide emulsion (AgI = 6 mole %;                                                             0.4 (Ag)                                           diameter/thickness ratio = 1.2; average grain                                 size = 1.0μ; AgI content is high at the                                    inner portion)                                                                Gelatin                    1.0                                                Sensitizing dye VII        3.5 × 10.sup.-4                              Sensitizing dye VIII       1.4 × 10.sup.-4                              Coupler C-13               0.01                                               Coupler C-12               0.03                                               Coupler C-9                0.20                                               Coupler C-1                0.02                                               Coupler C-15               0.02                                               Dispersion oil Oil-1       0.20                                               Dispersion oil Oil-2       0.05                                               ______________________________________                                        10th Layer: Yellow Filter Layer                                               Gelatin                    1.2                                                Yellow colloidal silver    0.08                                               Compound Cpd-B             0.1                                                Dispersion oil Oil-1       0.3                                                ______________________________________                                        11th Layer: First Blue-sensitive Emulsion Layer                               Monodisperse Silver iodobromide emulsion                                                                 0.4 (Ag)                                           (AgI = 4 mole %; diameter/thickness ratio = 1.5;                              average grain size = 0.5μ; AgI content is                                  high at the inner portion)                                                    Gelatin                    1.0                                                Sensitizing dye IX         2 × 10.sup.-4                                Coupler C-14               0.9                                                Coupler C-5                0.07                                               Dispersion oil Oil-1       0.2                                                ______________________________________                                        12th Layer: Second Blue-sensitive Emulsion Layer                              Silver iodobromide emulsion (AgI = 10 mole %;                                                            0.4 (Ag)                                           diameter/thickness ratio = 4.5; average grain                                 size = 1.3μ; AgI content is high at the                                    inner portion)                                                                Gelatin                    0.6                                                Sensitizing dye IX         1 × 10.sup.-4                                Coupler C-14               0.25                                               Dispersion oil Oil-1       0.07                                               ______________________________________                                        13th Layer: First Protective Layer                                            Gelatin                    0.8                                                Ultraviolet absorber UV-1  0.1                                                Ultraviolet absorber UV-2  0.2                                                Dispersion oil Oil-1       0.01                                               Dispersion oil Oil-2       0.01                                               ______________________________________                                        14th Layer: Second Protective Layer                                           Fine grain silver bromide (average grain                                                                 0.5                                                size = 0.07μ)                                                              Gelatin                    0.45                                               Polymethyl methacrylate particles                                                                        0.2                                                (diameter = 15μ)                                                           Film hardening agent H-1   0.4                                                n-Butyl p-hydroxybenzoate  0.012                                              Formaldehyde scavenger S-1 0.5                                                Formaldehyde scavenger S-2 0.5                                                ______________________________________                                    

To each layer there was added a surfactant as a coating aid in additionto the foregoing components.

The chemical structures or the chemical names of the compounds used inthis Example are as follows: ##STR27##

A multilayered color light-sensitive material (Sample 102) was preparedby applying in order coating solutions having the following compositionsonto the surface of a substrate of cellulose triacetate to which anunderlying layer had been applied.

Composition of the Light-sensitive Layer

In the following composition, the coated amounts are expressed in g/m²,that of silver halide is expressed in reduced amount of elementalsilver. The coated amount of sensitizing dyes is expressed in moles permole of silver halide included in the same layer.

    ______________________________________                                        (Sample 102)                                                                  ______________________________________                                        1st Layer: Halation Inhibiting Layer                                          Black colloidal silver     0.18 (Ag)                                          Gelatin                    0.40                                               ______________________________________                                        2nd Layer: Intermediate Layer                                                 2,5-Di-t-pentadecyl hydroquinone                                                                         0.18                                               EX-1                       0.07                                               EX-3                       0.02                                               EX-12                      0.002                                              U-1                        0.06                                               U-2                        0.08                                               U-3                        0.10                                               HBS-1                      0.10                                               HBS-2                      0.02                                               Gelatin                    1.04                                               ______________________________________                                        3rd Layer: First Red-sensitive Emulsion Layer                                 Monodisperse silver iodobromide emulsion                                                                 0.55 (Ag)                                          (AgI = 6 mole %; average grain size = 0.6μ;                                Coefficient of Variation in grain size                                        (C.V.) = 0.15)                                                                Sensitizing dye I          6.9 × 10.sup.-5                              Sensitizing dye II         1.8 × 10.sup.-5                              Sensitizing dye III        3.1 × 10.sup.-4                              Sensitizing dye IV         4.0 × 10.sup.-5                              EX-2                       0.350                                              HBS-1                      0.005                                              EX-10                      0.020                                              Gelatin                    1.20                                               ______________________________________                                        4th Layer: Second Red-sensitive Emulsion Layer                                Tabular silver iodobromide emulsion                                                                      1.0 (Ag)                                           (AgI = 10 mole %; average grain size = 0.7μ;                               average aspect ratio = 5.5; average                                           thickness = 0.2μ)                                                          Sensitizing dye I          5.1 × 10.sup.-5                              Sensitizing dye II         1.4 × 10.sup.-5                              Sensitizing dye III        2.3 × 10.sup.-4                              Sensitizing dye IV         3.0 × 10.sup.-4                              EX-2                       0.400                                              EX-3                       0.050                                              EX-10                      0.015                                              Gelatin                    1.30                                               ______________________________________                                        5th Layer: Third Red-sensitive Emulsion Layer                                 Silver iodobromide emulsion (AgI = 16 mole %;                                                            1.60 (Ag)                                          average grain size = 1.1μ)                                                 Sensitizing dye IX         5.4 × 10.sup.-5                              Sensitizing dye II         1.4 × 10.sup.-5                              Sensitizing dye III        2.4 × 10.sup.-4                              Sensitizing dye IV         3.1 × 10.sup.-5                              EX-3                       0.240                                              EX-4                       0.120                                              HBS-1                      0.22                                               HBS-2                      0.10                                               Gelatin                    1.63                                               ______________________________________                                        6th Layer: Intermediate Layer                                                 EX-5                       0.040                                              HBS-1                      0.020                                              EX-12                      0.004                                              Gelatin                    0.80                                               ______________________________________                                        7th Layer: First Green-sensitive Emulsion Layer                               Tabular silver iodobromide emulsion                                                                      0.40 (Ag)                                          (AgI = 6 mole %; average grain size = 0.6μ;                                average aspect ratio = 6.0; average                                           thickness = 0.15μ)                                                         Sensitizing dye I          3.0 × 10.sup.-5                              Sensitizing dye VI         1.0 × 10.sup.-4                              Sensitizing dye VII        3.8 × 10.sup.-4                              EX-6                       0.260                                              EX-1                       0.021                                              EX-7                       0.030                                              EX-8                       0.025                                              HBS-1                      0.100                                              HBS-4                      0.010                                              Gelatin                    0.75                                               ______________________________________                                        8th Layer: Second Green-sensitive Emulsion Layer                              Monodisperse silver iodobromide emulsion                                                                 0.80 (Ag)                                          (AgI = 9 mole %; average grain size = 0.7μ;                                Coefficient of Variation in grain size                                        (C.V.) = 0.18)                                                                Sensitizing dye V          2.1 × 10.sup.-5                              Sensitizing dye VI         7.0 × 10.sup.-5                              Sensitizing dye VII        2.6 × 10.sup.-4                              EX-6                       0.180                                              EX-8                       0.010                                              EX-1                       0.008                                              EX-7                       0.012                                              HBS-1                      0.160                                              HBS-4                      0.008                                              Gelatin                    1.10                                               ______________________________________                                        9th Layer: Third Green-sensitive Emulsion Layer                               Silver iodobromide emulsion (AgI = 12 mole %;                                                            1.2 (Ag)                                           average grain size = 1.0μ)                                                 Sensitizing dye V          3.5 × 10.sup.-5                              Sensitizing dye VI         8.0 × 10.sup.-5                              Sensitizing dye VII        3.0 × 10.sup.-4                              EX-6                       0.065                                              EX-11                      0.030                                              EX-1                       0.025                                              HBS-1                      0.25                                               HBS-2                      0.10                                               Gelatin                    1.74                                               ______________________________________                                        10th Layer: Yellow Filter Layer                                                Yellow colloidal silver   0.05 (Ag)                                          EX-5                       0.08                                               HBS-3                      0.03                                               Gelatin                    0.95                                               ______________________________________                                        11th Layer: First Blue-sensitive Emulsion Layer                               Tabular silver iodobromide emulsion                                                                      0.24 (Ag)                                          (AgI = 6 mole %; average grain size = 0.6μ;                                average aspect ratio = 5.7; average                                           thickness = 0.15μ)                                                         Sensitizing dye VIII       3.5 × 10.sup.-4                              EX-9                       0.85                                               EX-8                       0.12                                               HBS-1                      0.28                                               Gelatin                    1.28                                               ______________________________________                                        12th Layer: Second Blue-sensitive Emulsion Layer                              Monodisperse silver iodobromide emulsion                                                                 0.45 (Ag)                                          (AgI = 10 mole %; average grain size = 0.8μ;                               Coefficient of Variation in grain size                                        (C.V.) = 0.16)                                                                Sensitizing dye VIII       2.1 × 10.sup.-4                              EX-9                       0.20                                               EX-10                      0.015                                              HBS-1                      0.03                                               Gelatin                    0.46                                               ______________________________________                                        13th Layer: Third Blue-sensitive Emulsion Layer                               Silver iodobromide emulsion (AgI = 14 mole %;                                                            0.77 (Ag)                                          average grain size = 1.3μ)                                                 Sensitizing dye VIII       2.2 × 10.sup.-4                              EX-9                       0.20                                               HBS-1                      0.07                                               Gelatin                    0.69                                               ______________________________________                                        14th Layer: First Protective Layer                                            Silver iodobromide emulsion (AgI = 1 mole %;                                                             0.5 (Ag)                                           average grain size = 0.07μ)                                                U-4                        0.11                                               U-5                        0.17                                               HBS-1                      0.90                                               Gelatin                    1.00                                               ______________________________________                                        15th Layer: Second Protective Layer                                           Polymethylacrylate particles                                                                             0.54                                               (diameter = about 1.5μ)                                                    S-1                        0.15                                               S-2                        0.05                                               Gelatin                    0.72                                               ______________________________________                                    

To each layer, there were added, in addition to the foregoingcomponents, a gelatin hardening agent H-1 and a surfactant.

The structural formulas and chemical names of the compounds used in theforegoing compositions are as follows: ##STR28##

The same procedures as used for preparing Sample 101 were repeatedexcept that silver bromide emulsions were substituted for all of thesilver halide emulsions in Sample 101 to obtain Sample 103.

The color photographic light-sensitive materials (Samples 101 to 103)thus prepared each was exposed to light and then processed in accordancewith the following processes utilizing an automatic developing machinetill the cumulative amount of a bleach-fixing solution replenishedreached three times the volume of the tank for the mother liquorthereof.

    ______________________________________                                        Processing Method (A)                                                                   Process- Process-                                                             ing      ing      Amount    Volume                                            Time     Temp.    of        of Tank                                 Process   (sec)    (°C.)                                                                           replenisher                                                                             (1)                                     ______________________________________                                        Color Develop-                                                                          195      38       45        10                                      ment                                                                          Bleach-fixing                                                                           195      38       17        8                                       Water Washing                                                                           40       35       countercurrent                                                                          4                                       (1)                         flow system                                                                   from (2) to (1)                                   Water Washing                                                                           60       35       30        4                                       (2)                                                                           Stabilization                                                                           40       38       20        4                                       Drying    75       55       --        --                                      ______________________________________                                         *The amount replenished is expressed in milliliters per 1 m.sup.2 of the      processed lightsensitive material having a width of 35 mm.               

The composition of each processing solution is as follows:

    ______________________________________                                                             Tank Soln.                                                                              Replenisher                                    (Color Developer)    (g)       (g)                                            ______________________________________                                        Diethylenetriaminepentaacetic acid                                                                 1.0       1.1                                            1-Hydroxyethylidene-1,1-diphosphonic                                                               3.0       3.2                                            acid                                                                          Sodium sulfite       4.0       4.4                                            Potassium carbonate  30.0      37.0                                           Potassium bromide    1.4       0.7                                            Potassium iodide     1.5 (mg)  --                                             Hydroxylamine sulfate                                                                              2.4       2.8                                            4-(N-Ethyl-N-(β-hydroxyethyl)-amino)-                                                         4.5       5.5                                            2-methylaniline sulfate                                                       Water                ad. 1.0 l ad. 1.0 l                                      pH                   10.05     10.10                                          ______________________________________                                        (Bleach-fixing Solution): Tank Soln. and                                      Replenisher              Amount (g)                                           ______________________________________                                        Ferric ammonium ethylenediaminetetraacetate                                                            90.0                                                 dihydrate                                                                     Disodium ethylenediaminetetraacetate                                                                   5.0                                                  Sodium sulfite           6.0                                                  70% Aqueous solution of ammonium thiosulfate                                                           280                                                  p-Toluenesulfinic acid   20.0                                                 27% Aqueous ammonia      6.0 (ml)                                             Illustrated Compound IA-11                                                                             5 × 10.sup.-3 mole                             Water                    ad. 1.0 l                                            pH                       6.5                                                  ______________________________________                                    

Water Washing Solution Tank Soln. and Replenisher

This was prepared by passing tap water through a mixed bed column packedwith an H-type strong acidic cation-exchange resin (available from Rohm& Haas Co. Ltd. under the trade name of Amberlite IR-120B) and anOH-type anion-exchange resin (available from the same company under thetrade name of Amberlite IR-400) to reduce the concentrations of calciumand magnesium ions to a level of not more than 3 mg/l, respectively andthen adding 20 mg/l of sodium dichloroisocyanurate and 1.5 g/l of sodiumsulfate. The pH value of the solution was in the range of 6.5 to 7.5.

    ______________________________________                                        (Stabilization Solution): Tank Soln. and Replenisher                                                     Amount (g)                                         ______________________________________                                        37% Formalin               2.0 (ml)                                           Polyoxyethylene p-monononylphenyl ether                                                                  0.3                                                (average degree of polymerization = 10)                                       Disodium ethylenediaminetetraacetate                                                                     0.05                                               Water                      ad. 1.0 l                                          pH                         5.0-8.0                                            ______________________________________                                    

Then, a column packed with 1 l of a strong basic anion-exchange resin(Amberlite IRA-400) was incorporated into a piping of a circulatingpumping system for a bleach-fixing bath and Samples 101 to 103 werecontinuously processed (processing method B) as in the processing method(A).

In addition, the processing method (B) was performed without using theillustrated compound IA-11 (processing method (C)).

After each continuous processing, Samples 101 to 103 which had beenexposed to light (4000° K.; 100 CMS) were processed in an automaticdeveloping machine according to the process (A) or (B) and the amount ofresidual silver thereon was estimated by fluorescent X-rays technique.Moreover, unexposed Samples were processed to determine magenta density.

                  TABLE 1                                                         ______________________________________                                        Pro-            Amount of Residual                                                                          Magenta                                         cessing                                                                             Sample No.                                                                              Silver (μg/cm.sup.2)                                                                     Density                                         ______________________________________                                        A     103       8.7           0.38   Comp. Ex.                                A     102       15.4          0.46   "                                        A     101       20.7          0.48   "                                        B     103       9.3           0.32   "                                        B     102       2.4           0.28   Present                                                                       Invention                                B     101       1.9           0.27   Present                                                                       Invention                                C     103       9.0           0.32   Comp. Ex.                                C     102       7.0           0.30   "                                        C     101       5.3           0.30   "                                        ______________________________________                                    

The processing method of this invention provided good images having alow amount of residual silver and a low magenta density (stain) on theunexposed areas. Contrary to this, when Sample 103 free of iodide ionswas treated with the ion-exchange resin, almost no such effects couldnot be obtained. It is assumed that this effect of decreasing the amountof the residual silver is due to the removal of iodide ions accommodatedin the bleach-fixing solution through the treatment with theion-exchange resin, but the reason why the magenta stain was reduced isnot clear at present. The processing method of the present inventionmakes it possible to reduce the amount of the residual silver, in otherwords, to improve the bleaching ability of the processing and to bleachwithin a short time period.

Each of Samples was also processed at 38° C. for 4 min. 20 sec. using afixing solution N₃ for processing color negative film CN-16 Process(available from Fuji Photo Film Co., Ltd.). No change in the amount ofresidual Ag was observed.

EXAMPLE 2

A multilayered color light-sensitive material (Sample 201) was preparedby applying in order coating solutions having the following compositionson the surface of a substrate of cellulose triacetate to which anunderlying layer had been applied.

    ______________________________________                                        1st Layer: Halation lnhibiting Layer                                          Black colloidal silver   0.25 g/m.sup.2                                       Ultraviolet absorber U-1 0.1 g/m.sup.2                                        Ultraviolet absorber U-2 0.1 g/m.sup.2                                        High boiling point organic solvent Oil-1                                                               0.1 cc/m.sup.2                                       Gelatin                  1.9 g/m.sup.2                                        2nd Layer: First Intermediate Layer                                           Cpd                      10 mg/m.sup.2                                        High boiling point organic solvent Oil-3                                                               40 mg/m.sup.2                                        Gelatin                  0.4 g/m.sup.2                                        3rd Layer: Second Intermediate Layer                                          Surface fogged fine grain silver iodobromide                                                           0.05 g/m.sup.2 (Ag)                                  emulsion (average grain size = 0.06μ;                                      AgI content = 1 mole %)                                                       Gelatin                  0.4 g/m.sup.2                                        4th Layer: First Red-sensitive Emulsion                                       Layer                                                                         Silver iodobromide emulsion spectrally                                                                 0.4 g/m.sup.2 (Ag)                                   sensitized with sensitizing dyes S-1 and S-2                                  (1:1 mixture of monodisperse cubic grains having                              average grain size of 0.2μ and AgI content of                              5 mole % and monodisperse cubic grains having                                 average grain size of 0.1μ and AgI content of                              5 mole %)                                                                     Coupler C-1              0.2 g/m.sup.2                                        Coupler C-2              0.05 g/m.sup.2                                       High boiling point organic solvent Oil-1                                                               0.1 cc/m.sup.2                                       Gelatin                  0.8 g/m.sup.2                                        5th Layer: Second Red-sensitive Emulsion                                      Layer                                                                         Silver iodobromide emulsion spectrally                                                                 0.4 g/m.sup.2 (Ag)                                   sensitized with sensitizing dyes S-1 and S-2                                  (monodisperse emulsion of cubic grains having                                 average grain size of 0.3μ and AgI content of                              4 mole %)                                                                     Coupler C-1              0.2 g/m.sup.2                                        Coupler C-3              0.2 g/m.sup.2                                        Coupler C-2              0.05/g/m.sup.2                                       High boiling point organic solvent Oil-1                                                               0.1 cc/m.sup.2                                       Gelatin                  0.8 g/m.sup.2                                        6th Layer: Third Red-sensitive Emulsion Layer                                 Silver iodobromide emulsion spectrally                                                                 0.4 g/m.sup.2 (Ag)                                   sensitized with sensitizing dyes S-1 and S-2                                  (monodisperse cubic grains having average grain                               size of 0.4μ and AgI content of 2 mole %)                                  Coupler C-3              0.7 g/m.sup.2                                        Gelatin                  1.1 g/m.sup.2                                        7th Layer: Third Intermediate Layer                                           Dye D-1                  0.02 g/m.sup.2                                       Gelatin                  0.6 g/m.sup.2                                        8th Layer: Fourth Intermediate Layer                                          Surface fogged fine grain silver iodobromide                                                           0.05 g/m.sup.2 ( Ag)                                 emulsion (average grain size = 0.06μ;                                      AgI content = 1 mole %)                                                       Compound Cpd A           0.2 g/m.sup.2                                        Gelatin                  1.0 g/m.sup.2                                        9th Layer: First Green sensitive Emulsion Layer                               Silver iodobromide emulsion spectrally                                                                 0.5 g/m.sup.2 (Ag)                                   sensitized with sensitizing dyes S-3 and S-4                                  (1:1 mixture of monodisperse cubic grains having                              average grain size of 0.2μ and AgI content of                              5 mole % and monodisperse cubic grains having                                 average grain size of 0.1μ and AgI content of                              5 mole %)                                                                     Coupler C-4              0.3 g/m.sup.2                                        Compound Cpd B           0.03 g/m.sup.2                                       Gelatin                  0.5 g/m.sup.2                                        10th Layer: Second Green-sensitive                                            Emulsion Layer                                                                Silver iodobromide emulsion spectrally                                                                 0.4 g/m.sup.2 (Ag)                                   sensitized with sensitizing dyes S-3 and S-4                                  (monodisperse cubic grains having average grain                               size of 0.4μ and AgI content of 5 mole %)                                  Coupler C-4              0.3 g/m.sup.2                                        Compound Cpd B           0.03 g/m.sup.2                                       Gelatin                  0.6 g/m.sup.2                                        11th Layer: Third Green-sensitive Emulsion                                    Layer                                                                         Silver iodobromide emulsion spectrally                                                                 0.5 g/m.sup.2 (Ag)                                   sensitized with sensitizing dyes S-3 and S-4                                  (emulsion containing tabular grains having an                                 aspect ratio of 5, average grain size of                                      0.5μ and AgI content of 2 mole %)                                          Coupler C-4              0.8 g/m.sup.2                                        Compound Cpd B           0.08 g/m.sup.2                                       Gelatin                  1.0 g/m.sup.2                                        12th Layer: Fifth Intermediate Layer                                          Dye D-2                  0.05 g/m.sup.2                                       Gelatin                  0.6 g/m.sup.2                                        13th Layer: Yellow Filter Layer                                               Yellow colloidal silver  0.1 g/m.sup.2                                        Compound Cpd A           0.01 g/m.sup.2                                       Gelatin                  1.1 g/m.sup.2                                        14th Layer: First Blue-sensitive Emulsion Layer                               Silver iodobromide emulsion spectrally                                                                 0.6 g/m.sup.2 (Ag)                                   sensitized with sensitizing dyes S-5 and S-6                                  (1:1 mixture of monodisperse emulsion of cubic                                grains having average grain size of 0.2μ and                               AgI content of 3 mole % and monodisperse                                      emulsion of cubic grains having average grain                                 size of 0.1μ and AgI content of 3 mole %)                                  Coupler C-5              0.6 g/m.sup.2                                        Gelatin                  0.8 g/m.sup.2                                        15th Layer: Second Blue-sensitive                                             Emulsion Layer                                                                Silver iodobromide emulsion spectrally                                                                 0.4 g/m.sup.2 (Ag)                                   sensitized with sensitizing dyes S-7 and S-8                                  (emulsion containing tabular grains having an                                 aspect ratio of 7, average grain size of                                      0.5μ and AgI content of 2 mole %)                                          Coupler C-5              0.3 g/m.sup.2                                        Coupler C-6              0.3 g/m.sup.2                                        Gelatin                  0.9 g/m.sup.2                                        16th Layer: Third Blue-sensitive Emulsion                                     Layer                                                                         Silver iodobromide emulsion spectrally                                                                 0.4 g/m.sup.2  (Ag)                                  sensitized with sensitizing dyes S-7 and S-8                                  (emulsion containing tabular grains having an                                 aspect ratio of 7, average grain size of                                      1.0μ and AgI content of 2 mole %)                                          Coupler C-6              0.7 g/m.sup.2                                        Gelatin                  1.2 g/m.sup.2                                        17th Layer: First Protective Layer                                            Ultraviolet absorber U-1 0.04 g/m.sup.2                                       Ultraviolet absorber U-3 0.03 g/m.sup.2                                       Ultraviolet absorber U-4 0.03 g/m.sup.2                                       Ultraviolet absorber U-5 0.05 g/m.sup.2                                       Ultraviolet absorber U-6 0.05 g/m.sup.2                                       Compound Cpd C           0.8 g/m.sup.2                                        D-3                      0.05 g/m.sup.2                                       Gelatin                  0.7 g/m.sup.2                                        18th Layer: Second Protective Layer                                           Surface fogged fine grain silver iodobromide                                                           0.1 g/m.sup.2 (Ag)                                   emulsion (average grain size = 0.06μ;                                      AgI content = 1 mole %)                                                       Polymethyl methacrylate particles                                                                      0.1 g/m.sup.2                                        (average particle size = 1.5μ)                                             Polymethyl methacrylate-acrylic acid (4:6)                                                             0.1 g/m.sup.2                                        copolymer (average particle size = 1.5μ)                                   Silicone oil             0.03 g/m.sup.2                                       Fluorine containing surfactant W-1                                                                     3 mg/m.sup.2                                         Gelatin                  0.8 g/m.sup.2                                        ______________________________________                                    

In addition to the foregoing components, each composition furthercomprises a gelatin hardening agent H-1 and a surfactant. ##STR29##

The color photographic light-sensitive material (Sample 201) thusprepared was exposed to light and then processed according to thefollowing processes utilizing an automatic developing machine, in whichthe processing was continued till the cumulative amount of replenisherreached three times the volume of the tank for mother liquor.

    ______________________________________                                                 Process- Process-  Amount Re-                                                 ing time ing Temp. plenished                                                                              Volume of                                Process  (second) (°C.)                                                                            (ml/m.sup.2)                                                                           Tank (l)                                 ______________________________________                                        First    360      38        2200     12                                       development                                                                   First water                                                                            45       38        2200     2                                        washing                                                                       Reversal 45       38        1100     2                                        Color    360      38        2200     12                                       development                                                                   Bleaching                                                                              120      38         860     4                                        Bleach-fixing                                                                          240      38         360     8                                        Second water                                                                           60       38        --       2                                        washing (1)                                                                   Second water                                                                           60       38        1100     2                                        washing (2)                                                                   Stabilization                                                                          60       25        1100     2                                        Drying   60       65        --       --                                       ______________________________________                                         **The replenishing of the second water washing was performed according to     socalled countercurrent replenishment system in which a replenisher was       introduced into the water washing (2) and the overflow from the washing       (2) was introduced into the second water washing (1).                    

The composition of each processing solution is as follows:

    ______________________________________                                                          Tank Soln.  Replenisher                                     First Developer   (g)         (g)                                             ______________________________________                                        Pentasodium nitrilo-N,N,N-                                                                      2.0         2.0                                             trimethylene phosphonate                                                      Sodium sulfite    30          30                                              Potassium hydroquinone                                                                          20          20                                              monosulfonate                                                                 Potassium carbonate                                                                             33          33                                              1-Phenyl-4-methyl-4-hydroxy-                                                                    2.0         2.0                                             methy-3-pyrazolidone                                                          Potassium bromide 2.5         1.4                                             Potassium thiocyanate                                                                           1.2         1.2                                             Potassium iodide  1.2 (mg)                                                    Water             ad. 1,000 ml                                                                              ad. 1,000 ml                                    pH                9.60        9.60                                            ______________________________________                                         *pH was adjusted by the addition of hydrochloric acid or potassium            hydroxide.                                                               

    ______________________________________                                        First Washing Water: Tank Soln. and Replenisher                                                         Amount (g)                                          ______________________________________                                        Ethylenediaminetetramethylene phosphonic acid                                                           2.0                                                 Disodium hydrogen phosphate                                                                             5.0                                                 Water                     ad. 1,000 ml                                        pH                         7.00                                               ______________________________________                                         *pH was adjusted with hydrochloric acid or sodium hydroxide.             

    ______________________________________                                        Reversal Solution: Tank Solution and Replenisher                                                        Amount (g)                                          ______________________________________                                        Pentasodium nitrilo-N,N,N-trimethylene                                                                  3.0                                                 phosphonate                                                                   Tin (II) chloride dihydrate                                                                             1.0                                                 p-Aminophenol             0.1                                                 Sodium hydroxide          8                                                   Glacial acetic acid       15 (ml)                                             Water                     ad. 1,000 ml                                        pH                        6.00                                                ______________________________________                                         *pH was adjusted with hydrochloric acid or sodium hydroxide.             

    ______________________________________                                                           Tank Soln. Replenisher                                     Color Developer    (g)        (g)                                             ______________________________________                                        Pentasodium nitrilo-N,N,N-tri-                                                                   2.0        2.0                                             methylene phosphonate                                                         Sodium sulfite     7.0        7.0                                             Trisodium phosphate dodecahydrate                                                                36         36                                              Potassium bromide  1.0        --                                              Potassium iodide   90 (mg)    --                                              Sodium hydroxide   3.0        3.0                                             Citrazinic acid    1.5        1.5                                             N-Ethyl-N-(β-methanesulfon-                                                                 11         11                                              amidoethyl)-3-methyl-4-amino-                                                 aniline sulfate                                                               3,6-dithiaoctane-1,8-diol                                                                        1.0        1.0                                             Water              ad. 1,000 ml                                                                             ad. 1,000 ml                                    pH                 11.80      12.00                                           ______________________________________                                         *pH was adjusted by adding hydrochloric acid or potassium hydroxide.     

    ______________________________________                                        Bleaching Solution: Tank Solution and Replenisher                                                   Amount (g)                                              ______________________________________                                        Disodium ethylenediaminetetraacetate                                                                  10.0                                                  dihydrate                                                                     Ferric ammonium ethylenediaminetetraacetate                                                           120                                                   dihydrate                                                                     Ammonium bromide        100                                                   Ammonium nitrate        10                                                    Bleaching accelerator   0.005    (mole)                                        ##STR30##                                                                    Water                   ad. 1,000                                                                              ml                                           pH                      6.30                                                  ______________________________________                                         *pH was adjusted with hydrochloric acid or aqueous ammonia.              

    ______________________________________                                        Bleach-fixing Solution: Tank Solution and                                     Replenisher               Amount (g)                                          ______________________________________                                        Ferric ammonium ethylenediaminetetraacetate                                                             50                                                  dihydrate                                                                     Disodium ethylenediaminetetraacetate dihydrate                                                          5.0                                                 Sodium thiosulfate        80                                                  Sodium sulfite            12.0                                                Water                     ad. 1,000 ml                                        pH                        6.60                                                ______________________________________                                         *pH was adjusted with hydrochloric acid or aqueous ammonia.              

Second Water Washing Solution Tank Soln. & Replenisher

Tap water was passed through a mixed bed column packed with an H-typestrong acidic cation-exchange resin (available from Rohm & Hass Co.,Ltd. under the trade name of Amderlite IR-120B) and an OH-typeanion-exchange resin (available from the same company under the tradename of Amberlite IR-400) to reduce the concentrations of calcium andmagnesium ions to not more than 3 mg/l respectively and then 20 mg/l ofsodium dichloroisocyanurate and 1.5 g/l of sodium sulfate were addedthereto. The pH value of this solution was in the range of 6.5 to 7.5.

    ______________________________________                                        Stabilization Solution: Tank Soln. and                                        Replenisher              Amount (ml)                                          ______________________________________                                        37% Formalin             5.0                                                  Polyoxyethylene p-monononylphenyl ether                                                                0.5                                                  (average degree of polymerization = 10)                                       Water                    ad. 1,000 ml                                         pH                       not controlled                                       ______________________________________                                    

Then, continuous processing was performed by incorporating anion-exchange resin into the bleach-fixing bath as in Example 1 exceptthat the amount of the resin packed in a column was changed as in TableII in every processing. After the continuous processing, Sample 201which had been exposed to light (4800° K.; 100 CMS) was processed andthe amount of silver remaining on Sample was determined by means offluorescent X-rays technique.

                  TABLE II                                                        ______________________________________                                        Test No.                                                                             Amount of resin (1)                                                                         Amount of residual Ag (μg/cm.sup.2)                   ______________________________________                                         1*    0             15.6                                                     2      0.024         5.0                                                      3      0.24          4.8                                                      4      0.50          0.8                                                      5      1.00          0.3                                                      ______________________________________                                    

As seen from the results listed in Table II, when the ion-exchange resinwas used, the amount of the residual silver is low compared with thatobserved when it was not used and thus good results are obtained.

Each of Samples was also processed at 38° C. for 4 min. 20 seconds usinga fixing solution N₃ for processing color negative film CN-16 Process(available from Fuji Photo Film Co., Ltd.). There was observed no changein the amount of residual silver.

EXAMPLE 3

A color photographic light-sensitive material (Sample 301) was preparedby applying in order coating solutions for 1st to 12th layers having thefollowing compositions onto the surface of a paper subatrate whose bothsides had been laminated with polyethylene sheets. The polyethlene sheeton the side of the 1st layer contained titanium white as a white pigmentand a trace amount of Ultramarine Blue as a bluing dye.

Composition of the Light-sensitive Layer

The numerical values given below are the coated amount of each componentexpressed in g/m². The amount of coated silver halide is expressed inthe amount of elemental silver.

    ______________________________________                                        1st Layer: Gelatin Layer                                                      Gelatin                      1.30                                             2nd Layer: Antihalation Layer                                                 Black colloidal silver       0.10                                             Gelatin                      0.70                                             3rd Layer: Low Sensitive Red-sensitive Emulsion Layer                         Silver iodobromide spectrally sensitized                                                                   0.12                                             with red sensitizing dyes (*1 and *2)                                         (AgI = 4.0 mole %; average grain size =                                       0.4μ)                                                                      Gelatin                      1.00                                             Cyan coupler (*3)            0.14                                             Cyan coupler (*4)            0.07                                             Antidiscoloring agent (*5, *6 and *7)                                                                      0.10                                             Solvent for coupler (*8 and *9)                                                                            0.06                                             4th Layer: High Sensitive Red-sensitive Emulsion Layer                        Silver iodobromide spectrally sensitized                                                                   0.14                                             with red sensitizing dye (*1 and *2)                                          (AgI = 5.0 mole %; average grain size =                                       0.7μ)                                                                      Gelatin                      1.00                                             Cyan coupler (*3)            0.20                                             Cyan coupler (*4)            0.10                                             Antidiscoloring agent (*5, *6 and *7)                                                                      0.15                                             Solvent for coupler (*8 and *9)                                                                            0.10                                             5th Layer: Intermediate Layer                                                 Magenta colloidal silver     0.02                                             Gelatin                      1.00                                             Color mixing inhibitor (*10) 0.08                                             Solvent for color mixing inhibitor (*11 and *12)                                                           0.16                                             Polymer latex (*13)          0.10                                             6th Layer: Low Sensitive Green-sensitive Layer                                Silver iodobromide spectrally sensitized                                                                   0.09                                             with green sensitizing dye *14 (AgI =                                         2.0 mole %; grain size = 0.4μ)                                             Gelatin                      0.80                                             Magenta coupler (*15)        0.10                                             Antidiscoloring agent (*16)  0.10                                             Stain resistant agent (*17)  0.01                                             Stain resistant agent (*18)  0.001                                            Solvent for coupler (*11 and *19)                                                                          0.15                                             7th Layer: High Sensitive Green-sensitive Layer                               Silver iodobromide spectrally sensitized                                                                   0.09                                             with green sensitizing dye *14 (AgI =                                         3.0 mole %; grain size = 0.9μ)                                             Gelatin                      0.80                                             Magenta coupler (*15)        0.10                                             Antidiscoloring agent (*16)  0.10                                             Stain resistant agent (*17)  0.01                                             Stain resistant agent (*18)  0.001                                            Solvent for coupler (*11 and *19)                                                                          0.15                                             8th Layer: Yellow Filter Layer                                                Yellow colloidal silver      0.20                                             Gelatin                      1.00                                             Color mixing unhibitor (*10) 0.06                                             Solvent for Color mixing inhibitor (*11 and *12)                                                           0.15                                             Polymer latex (*13)          0.10                                             9th Layer: Low Sensitive Blue-sensitive Layer                                 Silver iodobromide spectrally sensitized                                                                   0.13                                             with blue sensitizing dye *20 (AgI =                                          2.0 mole %; grain size = 0.5μ)                                             Gelatin                      0.50                                             Yellow coupler (*21)         0.20                                             Stain resistant agent (*18)  0.001                                            Solvent for coupler (*9)     0.05                                             10th Layer: High Sensitive Blue-sensitive Layer                               Silver iodobromide spectrally sensitized                                                                   0.22                                             with blue sensitizing dye *20 (AgI =                                          2.5 mole %; grain size = 1.2μ)                                             Gelatin                      1.00                                             Yellow coupler (*21)         0.40                                             Stain resistant agent (*18)  0.002                                            Solvent for coupler (*9)     0.10                                             11th Layer: Ultraviolet Absorbing Layer                                       Gelatin                      1.50                                             Ultraviolet absorber (*22, *6 and *7)                                                                      1.00                                             Color mixing inhibitor (*23) 0.06                                             Solvent for color mixing inhibitor (*9)                                                                    0.15                                             Oxonol type irradiation inhibiting dye                                                                     0.02                                             Oxonol type irradiation inhibiting dye                                                                     0.02                                             12th Layer: Protective Layer                                                  Fine grain silver chlorobromide (AgCl =                                                                    0.07                                             97 mole %; average grain size = 0.2μ)                                      Gelatin                      1.50                                             Gelatin hardening agent (*26)                                                                              0.17                                             ______________________________________                                         (*1) Sodium salt of                                                           5,5'-Dichloro3,3'-di-(3-sulfobutyl)-9-ethylthiacarbonylcyanine;               (*2) Triethyl ammonium 3(2-(2-(3-(3-sulfopropyl)-naphtho(1,2-d)               thiazoline2-indenemethyl)-1-butenyl)-3-naphtho(1,2-d) thiazolino)propane      sulfonate;                                                                    (*3)                                                                          2(α-(2,4-di-t-amylphenoxy)-hexaneamido)-4,6-dichloro-5-ethylphenol;     (*4)                                                                          2(2-Chlorobenzoylamido)-4-chloro-5-(α-(2-chloro-4-t-amylphenoxy)-oc    aneamido)-phenol;                                                              (*5) 2(2-Hydroxy-3-sec-5-t-butylphenyl)-benzotriazole;                        (*6) 2(2-Hydroxy-5-t-butylphenyl)-benzotriazole;                              (*7) 2(2-Hydroxy-3,5-di-t-butylphenyl)-6-chloro-benzotriazole;                (*8) Dioctyl phthalate;                                                       (*9) Trinonyl phosphate;                                                      (*10) 2,5Di-t-octylhydroquinone;                                              (*11) Tricresyl phosphate;                                                    (*12) Dibutyl phthalate;                                                      (*13) Polyethyl acrylate;                                                     (*14) Sodium salt of                                                          5,5'-diphenyl9-ethyl-3,3'-disulfopropyl-oxacarbocyanine;                      (*15)                                                                         7Chloro-6-methyl-2-(1-(2-octyloxy-5-(2-octyloxy-5-t-octylbenzene-sulfonam    do)-2-propyl)-1H-pyrazolo(1,5-b) (1,2,4)triazole;                              (*16) 3,3,3',3'-Tetramethyl 15,6,5',6'-tetrapropoxy-1,1'-bis-spiroindane;     (*17) 3(2-Ethylhexyloxycarbonyloxy)-1-(3-hexadecyloxyphenyl)-2-pyrazoline     (*18) 2Methyl-5-t-octylhydroquinone;                                          (*19) Trioctyl phosphate;                                                     (*20) Triethyl ammonium                                                       3(2-(3-benzylrhodanin-5-ilydene)-3-benzoxazonyl)-propane sulfonate;           (*21)                                                                         α-pivaloylα-((2,4-dioxo-1-benzyl-5-ethoxyhydantoin-3-yl)-2-ch    oro-5-(α-2,4-di-t-amylphenoxy)-butaneamido)-acetanilide;                 (*22) 5Chloro-2-(2-hydroxy-3-t-butyl-5-t-octyl)-phenyl-benzotriazole;         (*23) 2,5Di-sec-octylhydroquinone;                                            (*24) 1,4Bis(vinylsulfonylacetamido)-ethane.                             

    ______________________________________                                        Process    Temp. (°C.)                                                                           Processing Time (sec)                               ______________________________________                                        First development                                                                        38             45                                                  (monochromatic                                                                development)                                                                  Water washing                                                                            38             45                                                  Reversal exposure                                                                        not less than 500 Lux                                                                        not less than 15                                    Color      38             60                                                  development                                                                   Water washing                                                                            38             15                                                  Bleach-fixing                                                                            38             60                                                  Water washing                                                                            38             60                                                  Drying     75             60                                                  ______________________________________                                    

    ______________________________________                                        Composition of Processing Solutions                                                                   Amount (g)                                            ______________________________________                                        [First Developer]                                                             Pentasodium nitrilo-N,N,N-trimethylene                                                                  0.6                                                 phosphonate                                                                   Pentasodium diethylenetriaminepentaacetate                                                              4.0                                                 Potassium sulfite         30.0                                                Potassium thiocyanate     1.2                                                 Potassium carbonate       35.0                                                Potassium hydroquinone monosulfonate                                                                    25.0                                                Diethylene glycol         15.0 (ml)                                           1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone                                                        2.0                                                 Potassium bromide         5.0 (mg)                                            Water                     ad. 1,000                                                                     (pH 9.7)                                            [Color Developer]                                                             Triethanolamine           8.0                                                 N,N-Diethylhydroxylamine  4.0                                                 3,6-Dithia-1,8-octanediol 0.2                                                 Disodium ethylenediaminetetraacetate dihydrate                                                          2.0                                                 Sodium sulfite            0.2                                                 Potassium carbonate       25.0                                                N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-                                                    8.0                                                 4-amino-aniline sulfate                                                       Potassium bromide         0.5                                                 Potassium iodide          0.1 (mg)                                            Water                     ad. 1,000                                                                     (pH 10.4)                                           [Bleach-fixing Solution]                                                      2-Mercapto-1,3,4-triazole 0.5                                                 Disodium ethylenediaminetetraacetate dihydrate                                                          5.0                                                 Ferric ammonium ethylenediaminetetraacetate                                                             80.0                                                monohydrate                                                                   Sodium sulfite            15.0                                                Sodium thiosulfate (700 g/l solution)                                                                   160.0                                               Glacial acetic acid       6.0                                                 Water                     ad. 1,000                                                                     (pH 6.0)                                            ______________________________________                                    

The silver halide color photographic light-sensitive material (Sample301) thus prepared was imagewise exposed to light and then processedaccording to the following processes utilizing an automatic developingmachine, in which the processing was continued till the cumulativeamount of replenisher reached three times the volume of the tanktherefor.

    ______________________________________                                                                             Volume of                                         Process- Process-  Amount Re-                                                                             Tank for                                          ing time ing Temp. plenished                                                                              Mother                                   Process  (second) (°C.)                                                                            (l/m.sup.2)                                                                            Liquor (1)                               ______________________________________                                        First    60       38        330      6                                        development                                                                   First water                                                                            30       33        --       3                                        washing (1)                                                                   First water                                                                            30       33        220      3                                        washing (2)                                                                   Color    90       38        330      9                                        development                                                                   Bleaching                                                                              60       38        120      6                                        Bleach-fixing                                                                          60       38         80      6                                        Second water                                                                           20       33        --       2                                        washing (1)                                                                   Second water                                                                           20       33        --       2                                        washing (2)                                                                   Second water                                                                           20       33        330      2                                        washing (3)                                                                   Drying   45       75        --       --                                       ______________________________________                                    

In the above processes, the first and second water washing process wereperformed by countercurrent replenishing system. More specifically, thefirst water washing solution was supplemented to first water washingbath (2) and the overflow from the water washing bath (2) was introducedinto the first water washing bath (1); on the other hand the secondwater washing solution was supplemented to the second water washing bath(3), the overflow from the bath (3) was introduced into the second waterwashing bath (2) and that from the latter was introduced into the secondwater washing bath (1).

The composition of each processing solution is as follows:

    ______________________________________                                        First Developer                                                                                  Tank Soln.                                                                              Replenisher                                                         (g)       (g)                                              ______________________________________                                        Pentasodium nitrilo-N,N,N-                                                                       1.0       1.0                                              trimethylene phosphonate                                                      Pentasodium diethylenetriamine-                                                                  3.0       3.0                                              pentaacetate                                                                  Potassium sulfite  30.0      30.0                                             Potassium thiocyanate                                                                            1.2       1.2                                              Potassium carbonate                                                                              35.0      35.0                                             Potassium hydroquinone                                                                           25.0      25.0                                             monosulfonate                                                                 1-Pheny1-3-pyrazolidone                                                                          2.0       2.0                                              Potassium bromide  0.5       --                                               Potassium iodide   5.0 (mg)                                                   Water              ad. 1,000 ad. 1,000                                        pH                 9.60      9.70                                             *pH was adjusted by the addition of hydrochloric acid or                      potassium hydroxide.                                                          ______________________________________                                        First Washing Water: Tank Soln. and Replenisher                                                        Amount (g)                                           ______________________________________                                        Ethylenediaminetetramethylene phosphonic acid                                                          2.0                                                  Disodium hydrogen phosphate                                                                            5.0                                                  Water                    ad 1,000                                             pH                       7.00                                                 *pH was adjusted with hydrochloric acid or sodium hydroxide.                  ______________________________________                                        Color Developer                                                                                  Tank Soln.                                                                              Replenisher                                                         (g)       (g)                                              ______________________________________                                        3,6-Dithio-1,8-octane-diol                                                                       2.00      2.50                                             Pentasodium nitrilo-N,N,N-tri-                                                                   0.5       0.5                                              methylene phosphonate                                                         Pentasodium diethylenetriamine-                                                                  2.0       2.0                                              pentaacetate                                                                  Triethylenediamine-1,4-diaza-                                                                    5.0       6.2                                              bicyclo(2,2,2)octane                                                          N-Ethyl-N-(β-methanesulfon-                                                                 6.0       9.0                                              amidoethy1)-3-methylamino-                                                    aniline sulfate                                                               Ethylenediamine    10.0      12.0                                             Fluorescent brightener (diamino-                                                                 1.0       1.2                                              stilbene type)                                                                Potassium bromide  0.5       --                                               Potassium iodide   1.0 (mg)  --                                               Water              ad. 1,000 ad. 1,000                                        pH                 10.60     11.00                                            *pH was adjusted by adding hydrochloric acid or potassium                     hydroxide.                                                                    ______________________________________                                        Bleaching Solution: Tank Solution and Replenisher                                                      Amount (g)                                           ______________________________________                                        Disodium ethylenediaminetetraacetate                                                                   10.0                                                 Ferric ammonium ethylenediaminetetraacetate                                                            120                                                  dihydrate                                                                     Ammonium bromide         100                                                  Ammonium nitrate         10                                                   Water                    ad. 1,000                                            pH                       6.30                                                 *pH was adjusted with acetic acid or aqueous ammonia.                         ______________________________________                                        Bleach-fixing Solution: Tank Solution and Replenisher                                                  Amount (g)                                           ______________________________________                                        Ferric ammonium ethylenediaminetetraacetate                                                            80.0                                                 monohydrate                                                                   Disodium ethylenediaminetetraacetate                                                                   5.0                                                  Ammonium thiosulfate (700 g/l)                                                                         160                                                  Sodium sulfite           15.0                                                 Bleaching accelerator    (see Table III)                                      Water                    ad. 1,000                                            pH                       6.50                                                 *pH was adjusted with acetic acid or aqueous ammonia.                         ______________________________________                                    

Second Water Washing Solution Tank Soln. & Replenisher

Tap water was passed through a mixed bed column packed with an H-typestrong acidic cation-exchange resin (available from Rohm & Hass Co.,Ltd. under the trade name of Amberlite IR-120B) and an OH-typeanion-exchange resin (available from the same company under the tradename of Amberlite IR-400) to reduce the concentrations of calcium andmagnesium ions to not more than 3 mg/l respectively and then 20 mg/l ofsodium dichloroisocyanurate and 1.5 g/l of sodium sulfate were addedthereto. The pH value of this solution was in the range of 6.5 to 7.5.

Moreover, a column packed with one liter of the ion-exchange resin wasincorporated into the bleach-fixing bath as in Example 1.

In the foregoing processing, continuous processing was performed whileadding bleaching accelerator to the bleach-fixing solution as shown inTable III. After the continuous processing, Sample 301 which was notexposed to light was processed and the amount of silver remaining onSample was determined.

                  TABLE III                                                       ______________________________________                                        Bleaching Accelerator                                                                           Amount added                                                                              Amount of Residual                              Test No.                                                                             Compound   (mole/l)    Ag (μg/cm.sup.2)                             ______________________________________                                         1*    --         --          5.4                                             2      (III)-(3)  0.005       1.7                                             3      (IV)-(1)   0.005       1.0                                             4       (V)-(1)   0.005       0.8                                             5      (III)-(5)  0.005       0.7                                             6      (IV)-(3)   0.005       1.2                                             ______________________________________                                         *Comparative Example.                                                    

As seen from Table III, good results (low residual silver) were obtainedwhen the bleaching accelerator was added to the bleach-fixing solution,since the bleaching ability of the bath was markedly enhanced.

Each of Samples was also processed as 38° C. for 4 min. 20 sec. using afixing solution N₃ for processing color negative films CN-16 Process(available from Fuji Photo Film Co., Ltd.). There was observed no changein the amount of residual silver.

EXAMPLE 4

A color photographic light-sensitive material (Sample 401) was preparedin the same manner as that for preparing Sample 301 except that theexemplary compound (I)-(2) was added to the first layer of Sample 301 inan amount of 1×10⁻⁴ mole per 1 m² of the light-sensitive material.Sample 401 was continuously processed according to the process No. 1 inExample 3. After the continuous processing, unexposed Sample 401 wasprocessed and it was found that the amount of residual silver was low(1.8 μg/cm²) which was better than that of Comparative Example (TableIII, No. 1; 5.4 μg/cm²).

Each of Samples was also processed as 38° C. for 4 min. 20 sec. using afixing solution N₃ for processing color negative films CN-16 Process(available from Fuji Photo Film Co., Ltd.). There was observed no changein the amount of residual silver.

EXAMPLE 5

Sample 103 prepared in Example 1 was continuously processed as inExample 1 utilizing a variety of anion-exchange resins listed in TableIV. The amount of residual silver of the resultant sample was determinedin the same manner as in Example 1.

                  TABLE IV                                                        ______________________________________                                                                Amount of Residual Silver                             Process No.                                                                            Anion-exchange resin                                                                         (μg/cm.sup.2)                                      ______________________________________                                         1*        --           16.5                                                  2        DIAION WA-20   10.3                                                  3        DIAION PA-318  3.5                                                   4        DIAION PA-418  3.0                                                   5        Exemplary Resin (34)                                                                         2.5                                                   6        Exemplary Resin (19)                                                                         1.0                                                   7        Exemplary Resin (1)                                                                          4.3                                                   8        Exemplary Resin (4)                                                                          0.5                                                   9        Exemplary Resin (48)                                                                         0.7                                                   10       Exemplary Resin (51)                                                                         0.8                                                   ______________________________________                                         *Comparative Example.                                                         **"DIAION" is the trade name of the anionexchange resins manufactured and     sold by MITSUBISHI CHEMICAL INDUSTRIES LTD.                              

As seen from the results listed in Table IV, good results (low residualsilver) were obtained when the anion-exchange resin of the presentinvention was used, since the bleaching ability of the processing bathwas markedly enhanced.

Each of Samples was also processed as 38° C. for 4 min. 20 sec. using afixing solution N₃ for processing color negative films CN-16 Process(available from Fuji Photo Film Co., Ltd.). There was observed no changein the amount of residual silver.

EXAMPLE 6

A multi-layered color light-sensitive material (Sample 601) was preparedby applying in order coating solutions having the following compositionson the surface of a substrate of cellulose triacetate to which anunderlying layer had been applied.

Composition of the light-sensitive Layer

The numerical values given below are the coated amount of each componentexpressed in g/m², that of silver halide is expressed in reduced amountof elemental silver. The coated amount of sensitizing dyes is expressedin moles per mole of silver halide included in the same layer.

    ______________________________________                                        1st Layer: Halation Inhibiting Layer                                          Black colloidal silver    0.2                                                 Gelatin                   1.0                                                 Ultraviolet absorber UV-1 0.05                                                Ultraviolet absorber UV-2 0.1                                                 Ultraviolet absorber UV-3 0.1                                                 Dispersion oil Oil-1      0.02                                                2nd Layer: Intermediate Layer                                                 Fine grain silver bromide (average grain                                                                0.15                                                size = 0.07μ)                                                              Gelatin                   1.0                                                 3rd Layer: First Red-sensitive Emulsion Layer                                 Emulsion A                1.42                                                Gelatin                   0.9                                                 Sensitizing dye A         2.0 × 10.sup.-4                               Sensitizing dye B         1.0 × 10.sup.-4                               Sensitizing dye C         0.3 × 10.sup.-4                               Cp-b                      0.35                                                Cp-c                      0.052                                               Cp-d                      0.047                                               D-1                       0.023                                               D-2                       0.035                                               HBS-1                     0.10                                                HBS-2                     0.10                                                4th Layer: Intermediate Layer                                                 Gelatin                   0.8                                                 Cp-b                      0.10                                                HBS-1                     0.05                                                5th Layer: Second Red-sensitive Emulsion Layer                                Emulsion B                1.38                                                Gelatin                   1.0                                                 Sensitizing dye A         1.5 × 10.sup.-4                               Sensitizing dye B         2.0 × 10.sup.-4                               Sensitizing dye C         0.5 × 10.sup.-4                               Cp-b                      0.150                                               Cp-d                      0.027                                               D-1                       0.005                                               D-2                       0.010                                               HBS-1                     0.050                                               HBS-2                     0.060                                               6th Layer: Third Red-sensitive Emulsion Layer                                 Emulsion E                2.08                                                Gelatin                   1.5                                                 Cp-a                      0.060                                               Cp-c                      0.024                                               Cp-d                      0.038                                               D-1                       0.006                                               HBS-1                     0.12                                                7th Layer: Intermediate Layer                                                 Gelatin                   1.0                                                 Cpd-A                     0.05                                                HBS-2                     0.05                                                8th Layer: First Green-sensitive Emulsion Layer                               Monodisperse silver iodobromide emulsion                                                                0.64                                                (Agl = 3 mole %; average grain size = 0.4μ;                                coefficient of variation = 19%)                                               Monodisperse silver iodobromide emulsion                                                                1.12                                                (AgI = 6 mole %; average grain size = 0.7μ;                                coefficient of variation = 18%)                                               Gelatin                   1.0                                                 Sensitizing dye D         1 × 10.sup.-4                                 Sensitizing dye E         4 × 10.sup.-4                                 Sensitizing dye F         1 × 10.sup.-4                                 Cp-f                      0.80                                                Cp-g                      0.084                                               Cp-k                      0.035                                               Cp-l                      0.036                                               D-3                       0.41                                                D-4                       0.018                                               HBS-1                     0.25                                                HBS-2                     0.45                                                9th Layer: Second Green-sensitive Emulsion Layer                              Monodisperse silver iodobromide emulsion                                                                2.07                                                (Agl = 7 mole %; average grain size = 1.0μ;                                Gelatin                   1.5                                                 Sensitizing dye D         1.5 × 10.sup.-4                               Sensitizing dye E         2.3 × 10.sup.-4                               Sensitizing dye F         1.5 × 10.sup.-4                               Cp-f                      0.02                                                Cp-g                      0.009                                               HBS-2                     0.088                                               10th Layer: Intermediate Layer                                                Gelatin                   1.2                                                 Yellow colloidal silver   0.06                                                Cpd-A                     0.3                                                 HBS-1                     0.3                                                 11th Layer: First Blue-sensitive Emulsion Layer                               Monodisperse silver iodobromide emulsion                                                                0.31                                                (AgI = 3 mole %; average grain size = 0.4μ;                                coefficient of variation = 20%)                                               Monodisperse silver iodobromide emulsion                                                                0.38                                                (AgI = 5 mole %; average grain size = 0.9μ;                                coefficient of variation = 17%)                                               Gelatin                   2.0                                                 Sensitizing dye G         1 × 10.sup.-4                                 Sensitizing dye H         1 × 10.sup.-4                                 Cp-i                      0.63                                                Cp-j                      0.57                                                D-1                       0.020                                               D-4                       0.015                                               HBS-1                     0.05                                                12th Layer: Second Blue-sensitive Emulsion Layer                              Monodisperse silver iodobromide emulsion                                                                0.77                                                (AgI = 8 mole %; average grain size = 1.3μ;                                coefficient of variation = 18%)                                               Gelatin                   0.5                                                 Sensitizing dye G         5 × 10.sup.-5                                 Sensitizing dye H         5 × 10.sup.-5                                 Cp-i                      0.10                                                Cp-j                      0.10                                                D-4                       0.005                                               HBS-2                     0.10                                                13th Layer: Intermediate Layer                                                Gelatin                   0.5                                                 Cp-m                      0.1                                                 UV-1                      0.1                                                 UV-2                      0.1                                                 UV-3                      0.1                                                 HBS-1                     0.05                                                HBS-2                     0.05                                                14th Layer: Protective Layer                                                  Monodisperse silver iodobromide emulsion                                                                0.1                                                 (AgI = 4 mole %; average grain size = 0.05μ;                               coefficient of variation = 10%)                                               Gelatin                   1.5                                                 Polymethyl methacrylate particles                                                                       0.1                                                 (average diameter = 1.5μ)                                                  S-1                       0.2                                                 S-2                       0.2                                                 ______________________________________                                    

To each layer, there were added a surfactant K-1 and gelatin hardeningagent H-1 in addition to the foregoing components. ##STR31##

Then, Samples 602 to 607 were prepared in the same manner as aboveexcept that the magenta coupler Cp-f used in the 8th and 9th layers wasreplaced with the following ones. These couplers were used in the samemolar amount. ##STR32##

Then, Sample 601 was imagewise exposed to light and continuouslyprocessed using an automatic developing machine according to thefollowing method until the cumulative amount of the bleach-fixingsolution replenished reached three times the volume of the tank for themother liquor therefor. In the bleach-fixing processing, the processings(methods 6-A to 6-D) were performed on cases wherein the bleachingaccelerator was present or absense or 1 l of the amino-exchange resinwas present or absense as in Example 1.

    ______________________________________                                        Processing Method (6-A)                                                                 Pro-     Pro-                                                                 cessing  cessing  Amount    Tank                                              Time     Temp.    Replenished                                                                             Volume                                  Process   (sec)    (°C.)                                                                           (ml)      (l)                                     ______________________________________                                        Color     195      38       45        10                                      development                                                                   Bleach-fixing                                                                           180      38       15        8                                       Stabilization (1)                                                                       20       35       countercurrent                                                                          4                                                                   piping system                                                                 from (2) to (1)                                   Stabilization (2)                                                                       20       35       countercurrent                                                                          4                                                                   piping system                                                                 from (3) to (2)                                   Stabilization (3)                                                                       20       35       20        4                                       Drying    75       55                                                         ______________________________________                                         *The amount replenished is expressed in the amount per 1 m of the             lightsensitive material having a wide of 35 mm.                          

The composition of each processing solution is as follows:

    ______________________________________                                                             Tank Soln.                                                                              Replenisher                                    (Color Developer)    (g)       (g)                                            ______________________________________                                        Diethylenetriaminepentaacetic acid                                                                 1.0       1.1                                            1-Hydroxyethylidene-1,1-diphosphonic                                                               3.0       3.2                                            acid                                                                          Sodium sulfite       4.0       4.4                                            Potassium carbonate  30.0      37.0                                           Potassium bromide    1.4       0.7                                            Potassium iodide     1.5 (mg)  --                                             Hydroxylamine sulfate                                                                              2.4       2.8                                            4-[N-Ethyl-N-(β-hydroxyethyl)amino]-                                                          4.5       5.5                                            2-methylamiline sulfate                                                       Water                ad. 1.0 l ad. 1.0 l                                      pH                   10.05     10.10                                          ______________________________________                                        (Bleach-fixing Solution): Tank Soln. & Replenisher                                                       (unit: g)                                          ______________________________________                                        Ferric ammonium ethylenediaminetetraacetate                                                              100.0                                              dihydrate                                                                     Disodium ethylenediaminetetraacetate                                                                     5.0                                                Sodium sulfite             6.0                                                70% aqueous solution of ammonium thiosulfate                                                             280                                                Paratoluonesulfinic acid   20.0                                               27% Aqueous ammonia        6.0 (ml)                                           Water                      ad. 1.0 l                                          pH                         6.5                                                ______________________________________                                        (Stabilization Solution): Tank Soln. & Replenisher                                                       (unit: g)                                          ______________________________________                                        Formalin (37%)             1.2 (ml)                                           5-Chloro-2-methyl-4-isothiazoline-3-one                                                                  6.0 (mg)                                           2-Methyl-4-isothiazolin-3-one                                                                            3.0 (mg)                                           Surfactant                 0.4                                                [C.sub.10 H.sub.21 --O--(CH.sub.2 CH.sub.2 O).sub.10 --H]                     Ethylene glycol            1.0                                                Water                      ad. 1.0 l                                          pH                         5.0 ˜ 7.0                                    ______________________________________                                    

Processing Method (6-B)

The processing (6-B) was the same as the processing method (6-A) exceptthat (IA)-(21) was added to the bleach-fixing solution as a bleachingaccelerator in an amount of 5×10⁻³ M.

Processing Method (6-C)

This was the same as the processing method (6-A) except that 1 l of theanion-exchange resin (3) was used in the bleach-fixing solution.

Processing Method (6-D)

This was the same as the processing method (6-A) except that (IA)-(21)as a bleaching accelerator and 1 l of the anion-exchange resin (3) wereused in the bleach fixing solution.

Then, Samples 601 to 607 were exposed to light through a continuous tonewedge and processed according to the processing methods (6-A) to (6-D)in a running state to determine the amount of residual silver onportions having the maximum density. In addition, after allowing theprocessed Samples to stand at 40° C./70% RH for one month, an increase(ΔD_(G) min.) in the magenta stain on portions having the minimumdensity. The results are listed in Table V.

                                      TABLE V                                     __________________________________________________________________________    Processing                                                                    6-A             6-B        6-C        6-D                                          Amount of  Amount of  Amount of  Amount of                                    silver     silver     silver     silver                                  Sample                                                                             (μg/cm.sup.2)                                                                    ΔD.sub.G min                                                                 (μg/cm.sup.2)                                                                    ΔD.sub.G min                                                                 (μg/cm.sup.2)                                                                    ΔD.sub.G min                                                                 (μg/cm.sup.2)                                                                    ΔD.sub.G                    __________________________________________________________________________                                                min                               601  15.1  +0.15                                                                              16.1  +0.15                                                                              8.5   +0.12                                                                              4.8   +0.10                             602  15.3  +0.16                                                                              15.8  +0.15                                                                              8.6   +0.14                                                                              4.7   +0.10                             603  15.6  +0.22                                                                              16.2  +0.21                                                                              8.8   +0.20                                                                              2.1   +0.09                             604  15.6  +0.20                                                                              16.3  +0.18                                                                              8.9   +0.19                                                                              2.0   +0.09                             605  16.0  +0.23                                                                              16.5  +0.21                                                                              9.0   +0.21                                                                              1.8   +0.08                             606  15.9  +0.25                                                                              16.5  +0.23                                                                              9.0   +0.23                                                                              1.8   +0.08                             607  15.8  +0.24                                                                              16.4  +0.21                                                                              9.1   +0.22                                                                              1.9   +0.07                             Note Comp. Ex.  Comp. Ex.  Comp. Ex.  Present Invention                       __________________________________________________________________________

The processing method of this invention (processing 6-D) is excellent indesilvering properties and lowers the increase in magenta density(magenta stain). In particular, Samples 603 to 607 in which preferredmagenta couplers were used show marked effects. Each of these Sampleswas processed at 38° C. for 4 min. 20 sec. using a fixing solution N3for processing color negative films CN-16 Process (available from FujiPhoto Film Co., Ltd.), but any change in the amount of residual silverwas not observed.

EXAMPLE 7

The same procedures as in Example 6 were repeated except that thebleaching accelerator (IA)-(21) used in processing 6-D of Example 6 wasreplaced with (IA)-(13), (IA)-(15), (IA)-(16), (VA)-(2), (VIA)-(1) or(VA)-(4). Thus, excellent effects were achieved.

EXAMPLE 8

The same procedures as in Example 6 (processing 6-D) were repeatedexcept that the ion-exchange resin (3) used in processing 6-D of Example6 was replaced with ion-exchange resin (4), (5), (19), (23), (44), (45),(49) or (51) and excellent effects were obtained.

We claim:
 1. A method for processing silver halide color photographiclight-sensitive materials which comprises color developing an image-wiseexposed silver halide color photographic light-sensitive material whichcontains at least one color coupler and which comprises a substrateprovided thereon with at least one silver halide emulsion layercontaining silver iodobromide and bleaching the light sensitivematerial, wherein the bleaching is performed in the presence of ableaching accelerator and the bleaching is carried out while a part orwhole of a bleaching solution is brought into contact with ananion-exchange resin so that the amount of iodide ions in the bleachingsolution is maintained at not more than 0.5 g/l expressed in the amountof KI.
 2. The method of claim 1 wherein the bleaching is performed usinga bleaching solution containing the anion-exchange resin.
 3. The methodof claim 1 wherein a part or whole of the used bleaching solution isbrought into contact with the anion-exchange resin and then used in thebleaching.
 4. The method of claim 1 wherein the silver iodobromidecontent of the silver halide emulsion layer is not less than 1 mole %.5. The method of claim 4 wherein the silver iodobromide content of thesilver halide emulsion layer ranges from 5 to 25 mole %.
 6. The methodof claim 1 wherein the anion-exchange resin is a basic anion-exchangeresin.
 7. The method of claim 6 wherein the basic anion-exchange resinis a strong basic anion-exchange resin.
 8. The method of claim 1 whereinthe bleaching treatment is a bleach-fixing treatment.
 9. The method ofclaim 1 wherein the amount of coated silver of the light-sensitivematerial ranges from 2 to 10 g/m².
 10. The method of claim 1 wherein thebleaching accelerator is an organic bleaching accelerator.
 11. Themethod of claim 10 wherein the bleaching accelerator is a compoundrepresented by the following general formula (IA):

    R.sup.1A --S--M.sup.1A                                     (IA)

(wherein M^(1A) represents a hydrogen atom, an alkali metal or anammonium residue; and R^(1A) represents an alkyl, alkylene, aryl orheterocyclic residue).
 12. The method of claim 1 wherein the content ofthe bleaching accelerator in the bleaching solution ranges from 1×10⁻⁵to 1×10⁻¹ mole/l.
 13. The method of claim 6 wherein the basicanion-exchange resin is a resin represented by the following generalformula (VIII): ##STR33## wherein A represents a monomer unit obtainedby copolymerizing copolymerizable monomers having at least twoethylenically unsaturated copolymerizable groups at least one of whichis present in a side chain; B represents a monomer unit obtained bycopolymerizing ethylenically unsaturated copolymerizable monomers; R₁₃represents a hydrogen atom, a lower alkyl group or an aralkyl group; Qrepresents a single bond, an alkylene, phenylene or aralkylene group, ora group represented by --CO--O--L--, --CO--NH--L-- or --CO--NR--L--(wherein L is an alkylene, arylene or aralkylene group and R is analkyl);G represents ##STR34## wherein R₁₄ to R₂₁ may be the same ordifferent and may be substituted and each represents a hydrogen atom, oran alkyl, aryl or aralkyl group; and X.sup.⊖ represents an anion, atleast two of Q, R₁₄, R₁₅ and R₁₆, or Q, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ maybe bonded to form a ring structure together with the nitrogen atom, x,yand z represent molar percentage, x ranges from 0 to 60, y from 0 to 60and z from 30 to 100).
 14. The method of claim 13 wherein the basicanion-exchange resin is a resin represented by the general formula (IX):##STR35## wherein A, B, x, y, z, R₁₃ to R₁₆ and X.sup.⊖ are the same asthose in the foregoing formula (VIII).
 15. The method of claim 13wherein G in the formula (VIII) is ##STR36##
 16. The method of claim 15wherein the total number of carbon atoms of R₁₄, R₁₅ and R₁₆ is not lessthan 12.